CN1788068A - Luminescent-polymer composition - Google Patents
Luminescent-polymer composition Download PDFInfo
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- CN1788068A CN1788068A CN 200480013076 CN200480013076A CN1788068A CN 1788068 A CN1788068 A CN 1788068A CN 200480013076 CN200480013076 CN 200480013076 CN 200480013076 A CN200480013076 A CN 200480013076A CN 1788068 A CN1788068 A CN 1788068A
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Abstract
A luminescent-polymer composition comprising a luminescent polymer and ion pairs, wherein the ion pairs each has an anion having such a specific structure that the anion has one atom of a Group 13 element and is bonded to either an aryl group having an electron-attracting group or a heterocyclic group having an electron-attracting group directly or through a connecting group or that the anion has two or more atoms of a Group 13 element and all these atoms each is bonded to either an aryl group having an electron-attracting group or a heterocyclic group having an electron-attracting group directly or through a connecting group.
Description
Technical field
The present invention relates to a kind of luminescent-polymer composition, a kind of luminescence polymer liquid composite and a kind of polymerization luminescent device (polymer LED) that uses them.
Background technology
Different with low molecular weight material, the luminescent material of pbz polymer amount (luminescence polymer) dissolves in the solvent, can form the luminescent layer of luminescent device by coating process, therefore meets the demand that forms broad area device.For this reason, in recent years, various polymer luminescent materials (for example, AdvancedMaterials Vol.12 1737-1750 (2000)) have been proposed.
Simultaneously, need luminescent device to have long work-ing life, that is, the brightness that causes by driving worsens little.
But when the material that uses luminescence polymer to use as the luminescent layer of luminescent device, the work-ing life of device is still unsatisfactory.
Summary of the invention
An object of the present invention is to provide a kind of polymkeric substance, it can obtain long-life luminescent device when being used for the luminescent layer of luminescent device.
As the result who furthers investigate in order to solve top problem, the inventor has found a kind of composition that comprises luminescence polymer and ion pair, described ion pair comprises: as anionic, with contain the aryl of electron withdrawing group, or the unit price heterocyclic radical that contains electron withdrawing group directly links to each other, or the 13rd family's atom that connects by linking group; Or comprise two or more the 13rd family's atoms, in these all atoms, each respectively with the aryl that contains electron withdrawing group, or the unit price heterocyclic radical that contains electron withdrawing group directly connects or connects by linking group; And found that the work-ing life of described device is elongated, and has finished the present invention when described composition is used as the material of luminescent device.
That is, the invention provides a kind of luminescent-polymer composition, it comprises luminescence polymer and ion pair, and the negatively charged ion of ion pair is represented by following formula (1a), (1b), (2) or (3):
(wherein, Y
1Represent the 13rd family's atom; Ar
1Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
1Expression Sauerstoffatom or direct key (direct bond); X
1Expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio, cyano group or the nitro of replacement; A represents 1 to 3 integer, and k represents 1 to 4 integer, V
1Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N=N-, or direct key; B represents 2 to 6 integer; And Z
1Expression-M ' (=O) p-(wherein, the atom of M ' expression the 3rd family, the 4th family, the 5th family, the 6th family, the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family, the 14th family, the 15th family, the 16th family or the 17th family; Represent 0 to 2 integer with p), or Z
1Expression b valency aliphatic alkyl, b valency aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N=N-,-NH-,-NH
2-,-OH-or direct key; But, work as Z
1For-C ≡ N-,-N=N=N-,-NH-,-NH
2-or-during OH-, b=2; Z
1And V
1Different mutually, work as Q
1And Ar
1Exist when a plurality of, they each other can be identical or different; A plurality of V
1Can be identical or different; C represents 1 to 6 integer),
(wherein, Y
2Represent the 13rd family's atom; Ar
2Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
2Expression Sauerstoffatom or direct key; X
2Expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio, cyano group or the nitro of replacement; D and d ' represent 1 or 2 independently of one another; V
2Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-or-N=N-; A plurality of Y
2, Ar
2, Q
2And V
2Can be identical or different; Work as X
2Exist when a plurality of, they can be identical or different; Represent 1 to 6 integer with e),
(wherein, Y
3Represent the 13rd family's atom; Ar
3Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
3Expression Sauerstoffatom or direct key; V
3Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-or-N=N-; A plurality of Y
3, Ar
3, Q
3And V
3Can be identical or different; Represent 1 to 6 integer with f).
Except top luminescent-polymer composition, the invention still further relates to a kind of luminescence polymer liquid composite, it also comprises solvent.
Embodiment
As for the ion pair that the present composition uses, negatively charged ion is by following formula (1a), (1b), (2) or (3) expression.
Y in formula (1a), (1b)
1Represent the 13rd family's atom, preferred boron, aluminium plus gallium, and more preferably boron.
Ar among formula (1a), (1b)
1Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group.
Contain electron withdrawing group and be meant a kind of atom or atomic group; it attracts electronics by resonance effect or influential action, and the example comprises halogen atom, nitro, nitroso-group, cyano group, acyl group, carboxyl, alkoxy carbonyl, aryloxycarbonyl, aryl-alkoxy carbonyl, heteroaryloxy carbonyl, perfluoroalkyl etc.
In electron withdrawing group, as for halogen atom, example be fluorine atom, chlorine atom, bromine atoms and iodine atom, and preferred fluorine atom.
Acyl group contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises ethanoyl, propionyl, butyryl radicals, isobutyryl, valeryl, benzoyl, trifluoroacetyl group, penta fluoro benzene formyl radical etc.
Alkoxy carbonyl contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, different-propoxycarbonyl, butoxy carbonyl, different-butoxy carbonyl, uncle-butoxy carbonyl, pentyloxy carbonyl, hexyloxy carbonyl, cyclohexyloxy carbonyl, heptan oxygen base carbonyl, carbonyl octyloxy, 2-ethyl hexyl oxy carbonyl, the ninth of the ten Heavenly Stems oxygen base carbonyl, the last of the ten Heavenly stems oxygen base carbonyl, 3,7-dimethyl-octa oxygen carbonyl, dodecane oxygen carbonyl, the trifluoromethoxy carbonyl, five fluorine ethoxy carbonyls, the perfluor butoxy carbonyl, the perfluor hexyloxy carbonyl, perfluor carbonyl octyloxy etc.
Aryloxycarbonyl contains 7 to 60 carbon atoms of having an appointment usually, and its specific examples comprises phenyloxycarbonyl, C
1-C
12Alkoxyl group phenyloxycarbonyl, C
1-C
12Alkyl phenoxy carbonyl, 1-naphthyloxy carbonyl, 1-naphthyloxy carbonyl, penta fluoro benzene oxygen base carbonyl etc.
Aryl-alkoxy carbonyl contains 8 to 60 carbon atoms of having an appointment usually, and its specific examples comprises phenyl-C
1-C
12Alkoxy carbonyl, C
1-C
12Alkoxyl phenyl-C
1-C
12Alkoxy carbonyl, C
1-C
12Alkyl phenyl-C
1-C
12Alkoxy carbonyl, 1-naphthyl-C
1-C
12Alkoxy carbonyl, 2-naphthyl-C
1-C
12Alkoxy carbonyl etc.
The heteroaryloxy carbonyl is (by Q
4-O (C=O)-group, and Q
4Expression unit price heterocyclic radical) contain 2 to 60 carbon atoms of having an appointment usually, and its specific examples comprises: thienyl oxygen base carbonyl, C
1-C
12Alkylthrophene base oxygen base carbonyl, pyrryl oxygen base carbonyl (pyroryloxycarbonyl), furyl oxygen base carbonyl, pyridyl oxygen base carbonyl, C
1-C
12Alkylpyridyl oxygen base carbonyl, imidazolyl oxygen base carbonyl, pyrazolyl oxygen base carbonyl, triazolyl oxygen base carbonyl, oxazolyl oxygen base carbonyl, thiazolyl oxygen base carbonyl, thiazoldiazolioxo carbonyl etc.
Perfluoroalkyl is meant straight chain, side chain or cyclic alkyl, wherein the hydrogen atom of all on alkyl is replaced by fluorine atom, and contain 1 to 20 carbon atom of having an appointment usually, and its specific examples comprise trifluoromethyl, perfluor ethyl, perfluoro propyl, seven fluorine different-propyl group, perfluoro butyl, trifluoro be different-butyl, 1,1-two (trifluoromethyl)-2,2,2 ,-trifluoroethyl, perfluor amyl group, perfluoro hexyl, perfluor cyclohexyl, perfluor heptyl, perfluoro capryl, perfluor nonyl, perfluor decyl, perfluor dodecyl etc.
Then,, explanation is contained the aryl of electron withdrawing group in formula (1a) with (1b), contain electron withdrawing group single Jie's heterocyclic radical, contain the aryloxy base of electron withdrawing group, contain single Jie's heteroaryloxy of electron withdrawing group.
The aryl that contains electron withdrawing group contains 6 to 60 carbon atoms of having an appointment usually, and its specific examples comprises phenyl, C
1-C
12Alkoxyl phenyl (C
1-C
12Expression carbonatoms 1-12, below identical), C
1-C
12Alkyl phenyl, 1-naphthyl, 2-naphthyl etc., it is replaced by one or more electron withdrawing groups recited above.
The unit price heterocyclic radical that contains electron withdrawing group contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises thienyl, C
1-C
12Alkylthrophene base, pyrryl, furyl, pyridyl, C
1-C
12Alkylpyridyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl, thiadiazolyl group etc., it is replaced by one or more electron withdrawing groups recited above.
Ar
1Specific examples comprise following group (I)-(V):
(I) contain the aryl of electron withdrawing group:
(II) contain the unit price heterocyclic radical of electron withdrawing group:
(III) contain fluorine atom or trifluoromethyl aryl as electron withdrawing group:
(IV) contain fluorine atom or trifluoromethyl unit price heterocyclic radical as electron withdrawing group:
(V) perfluor aryl, perfluor aryloxy:
The example of perfluor aryl comprises pentafluorophenyl group, seven fluoro-1-naphthyls, seven fluoro-2-naphthyls, nine fluoro-1-xenyls, nine fluoro-2-xenyls, nine fluoro-1-anthryls, nine fluoro-2-anthryls and nine fluoro-9-anthryls.
As for the aryl that contains electron withdrawing group with contain the unit price heterocyclic radical of electron withdrawing group, preferably contain those (top formulas (III), (IV) and (V)) of fluorine atom or trifluoromethyl, and more preferably perfluor aryl (last formula V).
At (1a) with the Q (1b)
1Expression Sauerstoffatom or direct key.
At (1a) with the X (1b)
1Expression expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio, cyano group or the nitro of replacement.
As for X
1In halogen atom, example be fluorine, chlorine, bromine and iodine.
Alkyl can be any in straight chain, side chain or the cyclic alkyl, and can contain one or more substituting groups.Carbonatoms is about 1 to 20 usually, and its specific examples comprises methyl, ethyl, propyl group, different-propyl group, butyl and different-butyl, tert-butyl, amyl group, hexyl, cyclohexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyl octyl group, dodecyl, trifluoromethyl, pentafluoroethyl group, perfluoro butyl, perfluoro hexyl, perfluoro capryl etc.
Alkoxyl group can be any in straight chain, side chain or the cyclic alkoxy and can contain one or more substituting groups.Carbonatoms is about 1 to 20 usually, and its specific examples comprises methoxyl group, oxyethyl group, propoxy-, different-propoxy-, butoxy, different-butoxy, uncle-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy, dodecyloxy, trifluoromethoxy, five fluorine oxyethyl groups, perfluor butoxy, perfluor hexyloxy, perfluor octyloxy, methoxymethyl oxygen base, 2-methoxy ethyl oxygen base etc.
Alkylthio can be any in straight chain, side chain or the ring-type alkylthio, and can have one or more substituting groups.Carbonatoms is about 1 to 20 usually, and its specific examples comprises methylthio group, ethylmercapto group, rosickyite base, different-the rosickyite base, butylthio, different-butylthio, uncle-butylthio, penta sulfenyl, own sulfenyl, hexamethylene sulfenyl, heptan sulfenyl, hot sulfenyl, 2-ethyl sulfenyl, ninth of the ten Heavenly Stems sulfenyl, last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl, dodecane sulfenyl, trifluoromethylthio etc.
Aryl can have one or more substituting groups.Carbonatoms is about 3 to 60 usually, and its specific examples comprises phenyl and C
1-C
12Alkoxyl phenyl (C
1-C
12Represent 1 to 12 carbonatoms, below identical), C
1-C
12Alkyl phenyl, 1-naphthyl, 2-naphthyl, pentafluorophenyl group etc.
Aryloxy can contain substituting group on aromatic ring.Carbonatoms is about 3 to 60 usually, and its specific examples comprises phenoxy group, C
1-C
12Alkoxyl group phenoxy group, C
1-C
12Alkyl phenoxy, 1-naphthyloxy, 2-naphthyloxy, penta fluoro benzene oxygen base etc.
Arylthio can contain substituting group on aromatic ring.Carbonatoms is about 3 to 60 usually, and its specific examples comprises thiophenyl, C
1-C
12Alkoxy benzene sulfenyl, C
1-C
12Alkyl sulfur-base, 1-naphthalene sulfenyl, 2-naphthalene sulfenyl, penta fluoro benzene sulfenyl etc.
Arylalkyl can contain substituting group, and carbonatoms is about 7 to 60 usually, and its specific examples comprises phenyl-C
1-C
12Alkyl, C
1-C
12Alkoxyl phenyl-C
1-C
12Alkyl, C
1-C
12Alkyl phenyl-C
1-C
12Alkyl, 1-naphthyl-C
1-C
12Alkyl, 2-naphthyl-C
1-C
12Alkyl etc.
Alkoxy aryl can contain substituting group, and carbonatoms is about 7 to 60 usually, and its specific examples comprises phenyl-C
1-C
12Alkoxyl group, C
1-C
12Alkoxyl phenyl-C
1-C
12Alkoxyl group, C
1-C
12Alkyl phenyl-C
1-C
12Alkoxyl group, 1-naphthyl-C
1-C
12Alkoxyl group, 2-naphthyl-C
1-C
12Alkoxyl group etc.
Alkylthio-aryl can contain substituting group, and carbonatoms is about 7 to 60 usually, and its specific examples comprises phenyl-C
1-C
12Alkylthio, C
1-C
12Alkoxyl phenyl-C
1-C
12Alkylthio, C
1-C
12Alkyl phenyl-C
1-C
12Alkylthio, 1-naphthyl-C
1-C
12Alkylthio, 2-naphthyl-C
1-C
12Alkylthio etc.
Alkenyl contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises vinyl, 1-propenyl, 2-propenyl, 3-propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and cyclohexenyl.
Alkenyl also comprises alkadienyl, for example the 1,3-butadiene base.
Alkynyl contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises ethynyl, 1-proyl, 2-propynyl, butynyl, pentynyl, hexin base, heptyne base, octyne base and cyclohexyl-acetylene base.The base of determining also comprises the alkane diynyl, for example 1, and 3-diacetylene base.
Aryl alkenyl contains 8 to 50 carbon atoms of having an appointment usually.Aryl and the alkenyl with above-mentioned is identical respectively with alkenyl for aryl in aryl alkenyl.Its specific examples comprises 1-aryl vinyl, 2-aryl vinyl, 1-aryl-1-propenyl, 2-aryl-1-propenyl, 2-aryl-2-propenyl, 3-aryl-2-propenyl etc.In addition, also comprise the aryl alkadienyl, for example 4-aryl-1,3-butadiene base.
Aromatic yl polysulfide yl contains 8 to 50 carbon atoms of having an appointment usually, and aryl and the alkynyl with above-mentioned is identical respectively with alkynyl for the aryl in aromatic yl polysulfide yl.Its specific examples comprises aryl ethane base, 3-aryl-1-proyl, 3-aryl-1-proyl etc.In addition, also comprise the aryl diynyl, 4-aryl-1 for example, 3-diacetylene base.
As for the siloxy-that replaces, example be the siloxy-(H that is selected from the group replacement in alkyl, aryl, arylalkyl and the unit price heterocyclic radical with 1,2 or 3
3SiO-).Alkyl, aryl, arylalkyl or unit price heterocyclic radical can contain substituting group.
The siloxy-that replaces contains 1 to 60 carbon atom of having an appointment usually, preferred about 3 to 30 carbon atoms, and its specific examples comprises trimethylsiloxy, silicoheptane alcoxyl base, three-just-propyl group siloxy-, three-different-propyl group siloxy-, tert-butyl silyl dimethylsilane oxygen base, triphenyl siloxy-, three-right-xylyl siloxy-, tribenzyl siloxy-, diphenyl methyl siloxy-, tert-butyl phenylbenzene siloxy-, 3,5-dimethylphenyl siloxy-.
As for the silylthio-that replaces, example be the silylthio-(H that is selected from the group replacement in alkyl, aryl, arylalkyl and the unit price heterocyclic radical with 1,2 or 3
3SiS-).Alkyl, aryl, arylalkyl or unit price heterocyclic radical can contain substituting group.
The silylthio-that replaces contains 1 to 60 carbon atom of having an appointment usually, preferred about 3 to 30 carbon atoms, and its specific examples comprises trimethyl silyl sulfenyl, silicoheptane alkylthio, three-just-propyl group silylthio-, three-different-propyl group silylthio-, tert-butyl silyl dimethylsilane sulfenyl, triphenyl silylthio-, three-right-xylyl silylthio-, tribenzyl silylthio-, diphenyl methyl silylthio-, tert-butyl phenylbenzene silylthio-, 3,5-dimethylphenyl silylthio-etc.
As for the silylamino-that replaces, example be the silylamino-(H that is selected from the group replacement in alkyl, aryl, arylalkyl and the unit price heterocyclic radical with 1 to 6
3SiNH-or (H
3Si)
2N-).Alkyl, aryl, arylalkyl or unit price heterocyclic radical can contain substituting group.
The silylamino-that replaces contains 1 to 120 carbon atom of having an appointment usually, preferred about 3 to 60 carbon atoms, and its specific examples comprises trimethyl silyl amino, the silicoheptane alkylamino, three-just-propyl group silylamino-, three-different-propyl group silylamino-, tert-butyl silyl dimethylsilane amino, the triphenyl silylamino-, three-right-xylyl silylamino-, the tribenzyl silylamino-, the diphenyl methyl silylamino-, tert-butyl phenylbenzene silylamino-, the 3,5-dimethylphenyl silylamino-, two (trimethyl silyl) amino, two (triethylsilyl) amino, two (three-just-propyl group silyl) amino, two (three-different-propyl group silyl) amino, two (tert-butyl silyl dimetylsilyl) amino, two (triphenyl silyl) amino, two (three-right-xylyl silyl) amino, two (tribenzyl silyl) amino, two (diphenyl methyl silyl) amino, two (tert-butyl diphenylmethyl silylation) amino, two (3,5-dimethylphenyl silyl) amino etc.
As for the amino that replaces, example be the amino that is selected from the group replacement in alkyl, aryl, arylalkyl and the unit price heterocyclic radical with 1 or 2.Alkyl, aryl, arylalkyl or unit price heterocyclic radical can contain substituting group.
The amino that replaces contains 1 to 40 carbon atom of having an appointment usually, and its specific examples comprises: methylamino, dimethylamino, ethylamino, diethylamino, propyl group amino, dipropyl amino, sec.-propyl amino, diisopropylaminoethyl, butyl amino, isobutylamino, tert-butyl amino, amyl group amino, hexyl amino, cyclohexyl amino, heptyl amino, octyl group amino, 2-ethylhexyl amino, nonyl amino, decyl amino, 3,7-dimethyl octyl group amino, dodecane amino, cyclopentyl amino, two cyclopentyl amino, cyclohexyl amino, dicyclohexyl amino, Pyrrolidine base (pyrrolidyl group), piperidyl, two (trifluoromethyl) amino, phenyl amino, diphenyl amino, C
1-C
12Alkoxyl phenyl amino, two (C
1-C
12Alkoxyl phenyl) amino, two (C
1-C
12Alkyl phenyl) amino, 1-naphthyl amino, 2-naphthyl amino, pentafluorophenyl group amino, pyridinylamino, pyridazinyl amino, pyrimidinyl-amino, pyrazine amino (pyrazylamino group), triazole amino, phenyl-C
1-C
12Alkylamino, C
1-C
12Alkoxyl phenyl-C
1-C
12Alkylamino, C
1-C
12Alkyl phenyl-C
1-C
12Alkylamino, two (C
1-C
12Alkoxyl phenyl-C
1-C
12Alkyl) amino, two (C
1-C
12Alkyl phenyl-C
1-C
12Alkyl) amino, 1-naphthyl-C
1-C
12Alkylamino, 2-naphthyl-C
1-C
12Alkylamino etc.
Amide group contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises formamido-, acetamido, propionamido-, amide-based small, benzoylamino, trifluoroacetyl amido, penta fluoro benzene formamido-, diformamide base, diacetylamino, dipropyl acidamide base, two amide-based smalls, dibenzoyl amido, two (trifluoroacetyl amido), two (penta fluoro benzene formamido-s) etc.
The example of acid imide base comprises the removed residue of the hydrogen atom that wherein is connected with nitrogen-atoms, and contains 2 to 60 carbon atoms of having an appointment usually, preferably contains 2 to 20 carbon atoms.As for the specific examples of acid imide base, example be following group:
Acyloxy contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, new pentane acyloxy, benzoyloxy, trifluoroacetyl oxygen base, penta fluoro benzene methanoyl etc.
The unit price heterocyclic radical is meant the atomic group of wherein removing hydrogen atom from heterogeneous ring compound.Carbonatoms is about 2 to 60 usually, and its specific examples comprises thienyl, C
1-C
12Alkylthrophene base, pyrryl, furyl, pyridyl, C
1-C
12Alkylpyridyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl, thiadiazolyl group etc.
The heterocycle aryloxy is (by Q
5The group that-O-represents, and Q
5Expression unit price heterocyclic radical) contain 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises thienyl oxygen base, C
1-C
12Alkylthrophene base oxygen base, pyrryl oxygen base, furyl oxygen base, pyridyl oxygen base, C
1-C
12Alkylpyridyl oxygen base, imidazolyl oxygen base, pyrazolyl oxygen base, triazolyl oxygen Ji, oxazolyl oxygen base, thiazolyl oxygen base, thiazoldiazolioxo etc.As for Q
5, preferred monovalent aromatic family heterocyclic radical.
The heterocycle arylthio is (by Q
6-S-represents.Q
6Expression unit price heterocyclic radical) contain 2 to 60 carbon atoms of having an appointment usually, and its specific examples comprises thienyl sulfydryl, C
1-C
12Alkylthrophene base-sulfydryl, pyrryl-sulfydryl, furyl sulfydryl, pyridyl sulfydryl, C
1-C
12Alkylpyridyl sulfydryl, imidazolyl sulfydryl, pyrazolyl sulfydryl, triazolyl sulfydryl, oxazolyl sulfydryl, thiazolyl sulfydryl, thiadiazolyl group sulfydryl etc.As for Q
6, preferred monovalent aromatic family heterocyclic radical.
In formula (1a), Z
1Expression-M ' (=O)
p-(wherein, the atom of M ' expression the 3rd family, the 4th family, the 5th family, the 6th family, the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family, the 14th family, the 15th family, the 16th family or the 17th family, represent 0 to 2 integer with p), or expression b-valency aliphatic alkyl, b-valency aliphatic alkyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N=N-,-NH-,-NH
2-,-OH-or direct key.But, work as Z
1For-C ≡ N-,-N=N=N-,-NH-,-NH
2-or-during OH-, b is 2.Though-C ≡ N-,-N=N=N-,-NH
2-and-OH-itself can charged positive lotus, the still description (Chem.Commun., 1999,1533) of omitting electric charge.
At Z
1For-M ' (=O)
p-situation under, as for the 3rd family among the M ', the 4th family, the 5th family, the 6th family, the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family, the 14th family, the 15th family, the atom of the 16th family and the 17th family, example be the boron atom, carbon atom, nitrogen-atoms, Sauerstoffatom, fluorine atom, the aluminium atom, Siliciumatom, phosphorus atom, sulphur atom, the chlorine atom, the scandium atom, titanium atom, vanadium atom, chromium atom, manganese atom, iron atom, cobalt atom, nickle atom, copper atom, zinc atom, the gallium atom, germanium atom, selenium atom, bromine atoms, yttrium atom, zirconium atom, molybdenum atom, the palladium atom, hafnium atom, tungsten atom, pt atoms etc., preferably nucleidic mass is 50 or following situation.
Be under the situation of atom of the 3rd family, the 4th family, the 5th family, the 6th family, the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family, the 14th family, the 15th family, the 16th family or the 17th family that do not comprise oxygen at M ', p can be 1, and working as M ' is the atomic time of the 5th family, the 6th family, the 7th family, and p can be 2.
As for the specific examples of p=1 or 2, example be-Ti (=O)-,-V (=O)-,-Cr (=O)-,-Cr (=O)
2-,-Zr (=O)-,-Mo (=O)-,-W (=O)-etc.
At Z
1In b-valency aliphatic hydrocarbon basis representation wherein from aliphatic hydrocarbon, remove the atomic group of b hydrogen atom, and can be straight chain, side chain or cyclic hydrocarbon group.It can contain substituting group, and carbonatoms is generally about 1 to 20 carbon atom.Though b is 2 to 6 integer, b is no more than the quantity of the hydrogen of aliphatic alkyl.
The specific examples of aliphatic hydrocarbon comprises methane, ethane, propane, cyclopropane, butane, tetramethylene, 2-methylpropane, pentane, pentamethylene, 2-methylbutane, 2,2-dimethylpropane, hexane, hexanaphthene, heptane, octane, 2-ethyl hexane, nonane, decane, 3,7-dimethyl octane etc.
The specific examples of divalence aliphatic alkyl (under the situation of b=2) comprising: methylene radical, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 1,3-cyclopentylidene, 1,4-cyclopentylidene etc.
Be not less than 3 and be no more than under 6 the situation at b, its specific examples comprises following group:
Z
1In b-valency aromatic hydrocarbons basis representation wherein from aromatic hydrocarbons, remove the atomic group of b hydrogen atom.It can contain substituting group on aromatic ring, carbonatoms is about 6 to 60 usually.B is no more than the quantity of hydrogen of the aromatic ring of aromatic hydrocarbyl.
The specific examples of aromatic hydrocarbons comprises benzene and C
1-C
12Alkoxy benzene (C
1-C
12The expression carbonatoms 1 to 12, below identical), C
1-C
12Alkylbenzene, naphthalene, anthracene, phenanthrene, tetracene, pentacene etc.
Under the situation of b=2 (divalence aromatic hydrocarbyl), the atomic group of two hydrogen atoms is wherein removed in its expression from aromatic hydrocarbyl, and carbonatoms is about 6 to 60 usually, is preferably 6 to 20.The example comprises phenylene (for example, following formula 1-3), naphthalene two bases (following formula 4-13), anthrylene (following formula 14-19), biphenylene (following formula 20-25), triphenylenyl (following formula 26-28), fused ring compound group (following formula 29-38) etc.The carbonatoms of substituent R is not counted the carbonatoms of divalence aromatic hydrocarbyl.
Each R represents hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; arylalkyl; alkoxy aryl; alkylthio-aryl; alkenyl; alkynyl; aryl alkenyl; aromatic yl polysulfide yl; the siloxy-that replaces; the silylthio-that replaces; the silylamino-that replaces; the amino that replaces; amide group; the acid imide base; acyloxy; the unit price heterocyclic radical; heteroaryloxy; heteroarylthio; acyl group; the imines residue; the silyl that replaces; alkoxy carbonyl; aryloxycarbonyl; aryl-alkoxy carbonyl; the heteroaryloxy carbonyl; carboxyl; cyano group or nitro.
Be under 3 to 6 the situation at b, as for b-valency aromatic hydrocarbyl, example be the residue of wherein from the example (1-38) of top divalence aromatic hydrocarbons, removing (b-2) individual R .
At Z
1In b-tooth heterocyclic radical be meant group derived from heterogeneous ring compound, and have b in conjunction with the position.As in conjunction with the position, example be with adjacent atom bonded position with by coordinate bond (coordinate bond part) bonded position by covalent linkage (covalent linkage part).
As for b-tooth heterocyclic radical, example be the b-tooth atomic group of wherein from heterogeneous ring compound, removing at least one hydrogen atom.They can contain substituting group, and it is about 2 to 60 that carbonatoms is generally, and is preferably 2 to 20.
As for bidentate heterocyclic radical (under the situation of b=2), example be to have the group of two covalent linkage parts (divalent heterocycle) and have a covalent linkage part and coordinate bond group of (unit price and bidentate heterocyclic radical) partly.As for the specific examples of divalent heterocycle, example be following:
Comprise nitrogen as heteroatomic divalent heterocycle; Pyridine-two base (following formula 39-44), diaza phenylene (following formula 45-48), quinoline two bases (following formula 49-63), quinoxaline two bases (following formula 64-68), acridine two bases (following formula 69-72), bipyridyl two bases (following formula 73-75), phenanthroline two bases (following formula 76-78) etc.
Have and comprise silicon, nitrogen, sulphur, selenium etc. as heteroatomic fluorene structured group (following formula 79-93).Consider luminous efficiency, preferably have the aromatic amine monomers that comprises nitrogen-atoms, for example the carbazole of formula 82-84 or triphenylamine two bases.
Comprise silicon, nitrogen, sulphur, selenium etc. as heteroatomic 5 yuan of heterocyclic radicals: (following formula 94-98).
Comprise silicon, nitrogen, sulphur, selenium etc. and condense 5 yuan of heterocyclic radicals: (following formula 99-109), diazosulfide-4,7-two bases, Ben Bing oxadiazole-4,7-two bases etc. as heteroatomic.
Comprise silicon, nitrogen, sulphur, selenium etc. as heteroatomic 5 yuan of heterocyclic radicals, it is connected to form dipolymer or oligopolymer (following formula 110-118) in heteroatomic position; With
Comprise silicon, nitrogen, sulphur, selenium etc. as heteroatomic 5 yuan of heterocyclic radicals, it is connected (following formula 112-118) with phenyl in heteroatomic position.
Wherein, R represents hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; arylalkyl; alkoxy aryl; alkylthio-aryl; alkenyl; alkynyl; aryl alkenyl; aromatic yl polysulfide yl; the siloxy-that replaces; the silylthio-that replaces; the silylamino-that replaces; the amino that replaces; amide group; the acid imide base; acyloxy; the unit price heterocyclic radical; heteroaryloxy; heteroarylthio; acyl group; the imines residue; the silyl that replaces; alkoxy carbonyl; aryloxycarbonyl; aryl-alkoxy carbonyl; the heteroaryloxy carbonyl; carboxyl; cyano group or nitro.
The specific examples of unit price and bidentate heterocyclic radical comprises: derived from the group of top 39-118 divalent heterocycle, one of them connecting key is replaced by R, and also contains coordinate bond on heteroatoms; And comprise following group:
When b is 3 to 6, as for b-valency heterocyclic radical (having b covalency part), example be the residue of wherein from the example of top divalent heterocycle, removing (b-2) individual hydrogen atom.
V in the formula (1a)
1Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N=N-or direct key, a plurality of V
1Can distinguish identical and different.Z
1And V
1Different.
At V
1In the example of the 16th family's atom comprise Sauerstoffatom, sulphur atom, selenium atom and tellurium atom, preferred oxygen atom and sulphur atom.
At V
1In definition and the specific examples and the top Z of divalence aliphatic alkyl
1In those are identical.
At V
1In definition and the specific examples and the top Z of divalence aromatic hydrocarbyl
1In those are identical.
At V
1In definition and the specific examples and the top Z of bidentate aliphatic alkyl
1In those are identical.
In formula (1a), a represents to be not less than 1 and be no more than 3 integer, is preferably 2 or 3, and more preferably 3.
In formula (1b), consider the device of making the long life, k represents to be not less than 1 and be no more than 4 integer, preferably is not less than 3 integer, and more preferably 4.
In formula (1a), b represents to be not less than 2 and be no more than 6 integer.But, work as V
1Be-C ≡ N-,-N=N=N-or directly during key, b is 2.
In formula (1a), c represents to be not less than 1 and be no more than 6 integer.
Anionic specific examples by following formula (1a) expression comprises the negatively charged ion of being represented by VI described below or VII:
In the middle of negatively charged ion, consider the long life, preferred Ar by following formula (1a) expression
1Be the situation of perfluor aryl, further preferably a is 2 or 3 situation.
More preferably Z
1Or V
1Situation for-C ≡ N-.Particularly, example is the negatively charged ion of being represented by following formula VII.
More preferably following formula (1a) is following formula (5-1) or situation (5-2):
[(C
6F
5)
3B-C≡N-B(C
6F
5)
3]
- (5-1)
[M{C≡N-B(C
6F
5)
3}
4]
2- (5-2)
(wherein, M represents nickle atom or palladium atom.)
In the middle of the negatively charged ion of following formula (1b) expression, consider the long life, preferred Ar
1Be the situation of perfluor aryl, more preferably k is 3 or 4 situation.
In the middle of negatively charged ion by formula (1b) expression, consider the long life, preferred Y is the situation of boron atom, more preferably it is the situation by (1b-1) expression:
(wherein, Ar
1, X represents and top identical implication with k.)
The situation of more preferably representing (1b-1) by following formula (1b-2):
[B(Ar
1b)
4]
- (1b-2)
(wherein, Ar
1bThe phenyl that expression is replaced by two or more groups that are selected from fluorine and the trifluoromethyl.Ar
1bCan be identical or different).
In the formula (1b-2), preferably all Ar
1bIt is identical situation.
As for example, example be by those of following formula (12) and (13) expression, preferably by those of formula (12) expression:
The situation of also preferably representing following formula (1b-1) by following formula (1b-3):
Wherein, X represents and top identical implication.Ar
1cRepresent the perfluor aryl and show 3 or 4 integer.
Particularly, inconvenience is following negatively charged ion:
As for the ion pair that the present composition uses, negatively charged ion is by following formula (1a), (1b), (2) or (3) expression.
In the middle of them, the negatively charged ion of formula (2) is represented:
(wherein, Y
2Represent the 13rd family's atom; Ar
2Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
2Expression Sauerstoffatom or direct key; X
2Expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio, cyano group or the nitro of replacement; D and d ' represent 1 or 2 independently of one another, V
2Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-or-N=N-; A plurality of Y
2, Ar
2, Q
2And V
2Can be identical or different; Work as X
2Exist when a plurality of, they can be identical or different; Represent 1 to 6 integer with e).
At Y
2In the specific examples and the top Y of the 13rd family's atom
1In those are identical.At Ar
2In contain the aryl of electron withdrawing group and contain definition and the specific examples and the Ar of the unit price heterocyclic radical of electron withdrawing group
1In those are identical.
At X
2In, the definition of the silylamino-of the siloxy-of halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, replacement, the silylthio-of replacement, replacement, the amino of replacement, amide group, acid imide, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio and specific examples and top X
2Those are identical.At V
2In, the definition of the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl and bidentate heterocyclic radical and specific examples and top V
1Those are identical.
As for the negatively charged ion by following formula (2) expression, specifically example is the negatively charged ion of being represented by following formula VIII:
In negatively charged ion, consider the long life, preferred Ar by following formula (2) expression
2Be the situation of perfluor aryl, more preferably Ar
2Be that perfluor aryl and d and d ' are 2 situations.
As for the ion pair that the present composition uses, by following formula (1a), (1b), (2) or (3) expression negatively charged ion, and in the middle of them, the negatively charged ion of formula (3) is represented:
(wherein, Y
3Represent the 13rd family's atom and Ar
3Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group.Q
3Expression Sauerstoffatom or direct key.V
3Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N-.A plurality of Y
3, Ar
3, Q
3, V
3Identical or different respectively.F represents 1 to 6 integer).
At Y
3In the specific examples and the top Y of the 13rd family's atom
1In those are identical, at Ar
3In contain the aryl of electron withdrawing group and contain definition and the specific examples and the Ar of the unit price heterocyclic radical of electron withdrawing group
1In those are identical.At V
3In, the definition of the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl and bidentate heterocyclic radical and specific examples and top V
1Those are identical.
As for the negatively charged ion by following formula (3) expression, specifically example is the negatively charged ion of being represented by following formula I X:
In following formula VI-IX, on aromatic hydrocarbons ring, heterocycle or hydrocarbon chain, can contain substituting group.
In negatively charged ion, consider the long life, preferred Ar by following formula (3) expression
3It is the situation of perfluor aryl.
In by following formula (1a), (1b), (2) or (3) expression negatively charged ion, preferably comprise anionic ion pair by formula (1a) expression.
The positively charged ion of the ion pair that comprises in the composition of the present invention then, is described.As for positively charged ion, example be: carbonium ion; Be selected from element in nitrogen-atoms, Sauerstoffatom, phosphorus atom, sulphur atom, chlorine atom, selenium atom, bromine atoms, tellurium atom and the iodine atom; Hydrogen ion and metallic cation.
Carbonium ion can be unit price or multivalence for example divalence or more than, and its specific examples comprises methyl (methylium), ethyl, neo-pentyl, cyclopropenyl radical, phenyl, anthryl and trityl group.
Nitrogen-atoms can be unit price or multivalence for example divalence or more than, and its specific examples comprises
The unit price aliphatics ammonium salt that is expressed from the next:
The cycloaliphatic ammonium salt that is expressed from the next:
The aromatic series ammonium salt that is expressed from the next:
The heterocyclic that comprises nitrogen-atoms that is expressed from the next:
Following formula (6)
Wherein, R
3And R
4Represent alkyl, alkoxyl group, aryl, aryloxy, arylalkyl, alkoxy aryl, acyl group, acyloxy, unit price heterocyclic radical or heteroaryloxy independently of one another.R
5And R
6Represent halogen atom independently of one another; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; arylalkyl; alkoxy aryl; alkylthio-aryl; alkenyl; alkynyl; aryl alkenyl; aromatic yl polysulfide yl; the siloxy-that replaces; the silylthio-that replaces; the silylamino-that replaces; the amino that replaces; amide group; the acid imide base; acyloxy; the unit price heterocyclic radical; heteroaryloxy; heteroarylthio; acyl group; the imines residue; the silyl that replaces; alkoxy carbonyl; aryloxycarbonyl; aryl-alkoxy carbonyl; the heteroaryloxy carbonyl; carboxyl; cyano group or nitro.T represents direct key, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, alkenylene, ethynylene or divalent heterocycle.I and j independently represent 0 to 4 integer separately.When there being two or more R
5And R
6The time, they can be identical or different.
At R
3, R
4, R
5And R
6In, the definition of the silylamino-of the siloxy-of halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, replacement, the silylthio-of replacement, replacement, the amino of replacement, amide group, acid imide, acyloxy, unit price heterocyclic radical, heteroaryloxy and heteroarylthio and specific examples and top X
1And X
2Those are identical.Acyl group, alkoxy carbonyl, aryloxycarbonyl, alkyl alkoxy carbonyl and heteroaryloxy carbonyl and top Ar
1, Ar
2And Ar
3In those of electron withdrawing group identical.
The imines residue is wherein (to contain molecule-organic compound of N=C-from group with imine moiety.Its specific examples comprises the compound that the hydrogen atom on aldimine, ketoimine and the N is replaced by alkyl etc.) in remove the residue of hydrogen atom, and contain 2 to 60 carbon atoms of having an appointment usually, preferred 2 to 20 carbon atoms.As for specific examples, example be the group of representing by following structural formula:
The silyl that replaces is represented by 1,2 or 3 silyl that is selected from the group replacement in alkyl, aryl, arylalkyl and the unit price heterocyclic radical.Carbonatoms is about 1 to 60 usually, is preferably 3 to 30.Alkyl, aryl, arylalkyl and unit price heterocyclic radical can contain substituting group.The example comprises trimethyl silyl, triethylsilyl, three-just-propyl group silyl, three-different-propyl group silyl, tert-butyl silyl dimetylsilyl, triphenyl silyl, three-right-xylyl silyl, tribenzyl silyl, diphenyl methyl silyl, tert-butyl diphenylmethyl silylation, 3,5-dimethylphenyl silyl etc.
The divalence aliphatic alkyl among the T of following formula (6) and the definition of divalence aromatic hydrocarbyl and specific examples and top V
1, V
2, V
3Those are identical.
Divalent heterocycle is meant wherein the atomic group of removing two hydrogen atoms from heterogeneous ring compound, and carbonatoms is about 2 to 60 usually, is preferably 2 to 20.On divalent heterocycle, can comprise substituting group, and substituent carbonatoms is not counted divalence heterocyclic carbonatoms.
As for the specific examples of divalent heterocycle, example be to be top Z
1And those of example.
Alkenylene contains 2 to 20 carbon atoms of having an appointment usually, and its specific examples comprises vinylene, propenylidene etc.Alkenylene comprises alkadienylene, for example 1, and 3-Aden dialkylene.
Alkynylene contains 2 to 20 carbon atoms of having an appointment usually, and the example comprises ethynylene etc.Alkynylene also comprises having two triple-linked groups, for example 1, and 3-Aden diynyl.
As for the specific examples of formula (6), example be following:
Consider luminous intensity, the positively charged ion that preferred ion is right is the situation by the divalent cation of formula (6) expression.
Sauerstoffatom can be unit price, multivalence for example divalence or more than, the example comprises trimethylammonium oxygen, triethyl oxygen, tripropyl oxygen, tributyl oxygen, three hexyl oxygen, triphenyl oxygen, pyrroline (pyrrylinium), chromene and xanthene.
Phosphorus atom can be unit price, multivalence for example divalence or more than, the example comprises tetramethyl phosphonium, four second base Phosphonium, 4 third basic Phosphonium, 4-butyl-phosphonium, four oneself basic Phosphonium, tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium and first base triphenyl phosphonium.
Sulphur atom can be unit price, multivalence for example divalence or more than, the example comprises the aliphatics sulfonium, for example trimethylsulfonium, triethyl sulfonium, tripropyl sulfonium, tributyl sulfonium and three hexyl sulfoniums; Aromatic matte, for example triphenylsulfonium, three (4-aminomethyl phenyl) sulfonium and three (4-tert-butyl phenyl) sulfonium, methyldiphenyl base sulfonium, 3,5-dimethylphenyl sulfonium and following formula:
The chlorine atom can be unit price, multivalence for example divalence or more than, the example comprises dimethyl chloride (chloronium), diethyl chlorine, dipropyl chlorine, dibutyl chlorine, phenylbenzene chlorine and aminomethyl phenyl chlorine.
Selenium atom can be unit price, multivalence for example divalence or more than, the example comprises trimethylammonium selenium, triethyl selenium, tripropyl selenium, tributyl selenium, three hexyl selenium, triphenyl selenium, three (4-aminomethyl phenyl) selenium, three (4-tert-butyl phenyl) selenium, methyldiphenyl base selenium and 3,5-dimethylphenyl selenium.
Bromine atoms can be unit price, multivalence for example divalence or more than, the example comprises dimethyl bromine (bromonium), diethyl bromine, dipropyl bromine, dibutyl bromine, phenylbenzene bromine and aminomethyl phenyl bromine.
Tellurium atom can be unit price, multivalence for example divalence or more than, the example comprises trimethylammonium tellurium, triethyl tellurium, tripropyl tellurium, tributyl tellurium, three hexyl telluriums, triphenyl tellurium, three (4-aminomethyl phenyl) tellurium, three (4-tert-butyl phenyl) tellurium, methyldiphenyl base tellurium, 3,5-dimethylphenyl tellurium.
The iodine atom can be unit price, multivalence for example divalence or more than, the example comprises dimethyl iodine, diethyl iodine, dipropyl iodine, dibutyl iodine, phenylbenzene iodine, two (tert-butyl phenyl) iodine, 4-aminomethyl phenyl-4-(1-methylethyl) phenyl-iodide, aminomethyl phenyl iodine or following formula:
The example of metallic cation comprises alkali metal cation, alkaline earth metal cation, yttrium positively charged ion, transition-metal cation etc., and they can be unit prices, or multivalence for example divalence or more than.
Because because the sudden fire of light of heavy atom effect may take place, preferred nucleidic mass is lower than 50.
The specific examples of alkali metal cation comprises lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and francium ion.
The specific examples of alkaline earth metal cation comprises beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, (MgCl)
+, (MgBr)
+(MgI)
+
The cationic specific examples of yttrium comprises scandium ion and ruthenium ion.The specific examples of transition-metal cation comprises titanium ion, zirconium ion, hafnium ion, vanadium ion, chromium ion, [two (η
5-benzene) Cr]
+, mn ion, iron ion, [(η
5-cyclopentadienyl) (η 6
-Benzene) Fe]
+, [(η
5-cyclopentadienyl) (η
6-toluene) Fe]
+[(η
5-cyclopentadienyl) (η
6-1-methylnaphthalene) Fe]
+, [(η
5-cyclopentadienyl) (η
6-cumene) Fe]
+, [two (η
5-1) Fe]
+, cobalt ion, nickel ion, cupric ion, zine ion etc.
As for ion pair of the present invention, enumerate following compound especially:
As for positively charged ion is those of carbonium ion, enumerates following ion pair:
As for positively charged ion be nitrogen-atoms those, example be those of aromatic series ammonium salt, those of aliphatics ammonium salt, those of those of aromatic series amine salt and aromatic series diazonium salt.The example of those of aromatic series ammonium salt comprises 1-benzyl-2-cyanopyridine four (pentafluorophenyl group) borate, 1-(naphthyl methyl)-2-cyanopyridine four (pentafluorophenyl group) borate, N, accelerine four (pentafluorophenyl group) borate, 1-butyl-3-Methylimidazole four (pentafluorophenyl group) borate, 1-ethyl-3-Methylimidazole four (pentafluorophenyl group) borate, 1-octyl group-3-Methylimidazole four (pentafluorophenyl group) borate, three (4-bromophenyl) ammonium four (pentafluorophenyl group) borates.
The example of those of aliphatics ammonium salt comprises TBuA four (pentafluorophenyl group) borate, tetraethyl ammonium four (pentafluorophenyl group) borate.
The example of those of aromatic series amine salt comprises three (4-bromophenyl) ammonium, four (pentafluorophenyl group) borate, N, N, N ', N '-tetraphenyl-4,4 '-biphenylene, two ammonium four (pentafluorophenyl group) borates.
The example of those of aromatic series diazonium salt comprises phenyl diazonium four (pentafluorophenyl group) borate.
The example of those of aromatic series ammonium salt comprises the new compound by following formula (10) expression:
Wherein, R
3, R
4, R
5, R
6Represent and top identical implication with T.
As for compound by following formula (10) expression, example be following compound:
Compound by following formula (10) expression can be by the compound and the Li[B (C of for example following formula (11) expression
6F
5)
4] n (Et
2O) reaction prepares:
[wherein, R
3, R
4, R
5, R
6Represent and top identical implication with T.X
1-And X
2-Independent separately expression halide-ions, alkyl sulfonate ion and aryl sulfonic acid radical ion.]
As for halide-ions, example be fluorion, chlorion, bromide anion and iodide ion.
As for alkyl sulfonate ion, example be methanesulfonic radical ion, ethane sulfonic acid radical ion, trifluoromethayl sulfonic acid radical ion.
As for the aryl sulfonic acid radical ion, example be Phenylsulfonic acid radical ion and right-toluenesulphonic acids radical ion.
As for the aromatic series ammonium salt those, example is following ion pair in addition:
As for the aliphatics ammonium salt those, example is following ion pair in addition:
As for the aromatic series amine salt those, example is following ion pair in addition:
As for the aromatic series diazonium salt those, example is following ion pair in addition:
As for positively charged ion be phosphorus atom those, example be tetraphenylphosphoniphenolate four (pentafluorophenyl group) borate.As for positively charged ion be phosphorus atom those, example is following ion pair in addition:
As for positively charged ion be sulphur atom those, example be those of aromatic series sulfonium salt.The example comprises two [4-(phenylbenzene sulfonium base) phenyl] sulfide four (pentafluorophenyl group) borate, phenylbenzene-4-(thiophenyl) phenyl sulfonium four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, two [4-(two (4-(2-hydroxyl-oxethyl) phenyl sulfonium base) phenyl] sulfide four (pentafluorophenyl group) borate].As for positively charged ion be sulphur atom those, example is following ion pair in addition:
As for positively charged ion be the iodine atom those, example be those of aromatic series salt compounded of iodine.The example comprises phenylbenzene iodine four (pentafluorophenyl group) borate, two (dodecylphenyl) iodine four (pentafluorophenyl group) borate, 4-aminomethyl phenyl-4-(1-methylethyl) phenyl-iodide four (pentafluorophenyl group) borate [" Rhodrsil light trigger PI-2074 " Photoepolymerizationinitiater initiater is purchased from Rhodia].As for positively charged ion be the iodine atom those, example is following ion pair in addition:
As for positively charged ion is those of metallic cation, and the example comprises (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene]-Fe (II) four (pentafluorophenyl group) borate.As for positively charged ion is those of metallic cation, and example is following ion pair in addition:
Li
+[(C
6F
5)
3B-≡N-B(C
6F
5)
3]
- K
+[(C
6F
5)
3B-≡N-B(C
6F
5)
3]
- Na
+[(C
6F
5)
3B-≡N-B(C
6F
5)
3]
-
MgB
r+[(C
6F
5)
3B-≡N-B(C
6F
5)
3]
- 
The invention provides a kind of new ion pair, wherein negatively charged ion is represented by following structural formula (5-1), and positively charged ion is pyridylium, phosphonium cation or iodine positively charged ion:
[(C
6F
5)
3B-C≡N-B(C
6F
5)
3] (5-1)
Specific examples is schematically as follows:
As for positively charged ion is the ion pair of pyridylium, example be following compound:
As for the ion pair of positively charged ion Shi phosphonium cation, example be following compound:
As for positively charged ion is the cationic ion pair of iodine, example be following compound:
For example, pyridinium salt, phosphonium salt recited above and salt compounded of iodine can be by compound and the K[(C by following formula (7-1) expression
6F
5)
3B-C ≡ N-B (C
6F
5)
3] reaction prepare:
E
1+X
1- (7-1)
Wherein, E
1+Expression pyridylium, phosphonium cation or iodine positively charged ion.X
1-Expression halide-ions, alkyl sulfonate ion and aryl sulfonic acid radical ion.
As for halide-ions, example be fluorion, chlorion, bromide anion and iodide ion (iodationthing).
As for alkyl sulfonate ion, example be methanesulfonic radical ion, ethane sulfonic acid radical ion and trifluoromethayl sulfonic acid radical ion.
As for the aryl sulfonic acid radical ion, example be Phenylsulfonic acid radical ion and right-toluenesulphonic acids radical ion.
The invention provides a kind of new ion pair, wherein negatively charged ion is pyridylium, quaternary ammonium cation, phosphonium cation, oxygen positively charged ion, sulfonium cation or iodine positively charged ion by following structural formula (5-2) expression and positively charged ion:
[M{C≡N-B(C
6F
5)
3}
4]
2- (5-2)
(wherein, M represents nickle atom or palladium atom.)
Specific examples schematically as follows.
As for positively charged ion is the ion pair of pyridylium, example be following compound:
As for positively charged ion is the ion pair of quaternary ammonium cation, example be following compound:
As for the ion pair of positively charged ion Shi phosphonium cation, example be following compound:
As for positively charged ion is the cationic ion pair of oxygen, example be following compound:
As for positively charged ion is the ion pair of sulfonium cation, example be following compound:
As for positively charged ion is the cationic ion pair of iodine, example be following compound:
For example, pyridinium salt, phosphonium salt recited above and salt compounded of iodine can pass through the compound and the K of following formula (7-2) expression
2[M{C ≡ N-B (C
6F
5)
3}
4] reaction prepare:
E
2+X
2- (7-2)
Wherein, E
2+Expression pyridylium, quaternary ammonium cation, phosphonium cation, oxygen positively charged ion, sulfonium cation or iodine positively charged ion.X
2-Expression halide-ions, alkyl sulfonate ion and aryl sulfonic acid radical ion.
As for the specific examples of halide-ions, alkyl sulfonate ion and aryl sulfonic acid radical ion, can example be to be used for top X
1-Ion.
In the present invention, to the ion pair that luminescent-polymer composition adds can be any two kinds or more than.
Then, explanation is used for luminescence polymer of the present invention.
The number-average molecular weight that is used for the polystyrene conversion of luminescence polymer of the present invention is generally 10
3-10
8In luminescence polymer of the present invention, preferred conjugated polymers compounds.The conjugated polymers compounds is meant that there is the right polymer compound of displacement πDian Zi in the main chain together with polymer compound.As for metastasic electron, sharing electron or lone electron pair can not replace two keys to participate in resonance.
What be used for luminescence polymer of the present invention can be homopolymer or multipolymer, and the example comprises: and poly-fluorenes [for example, Jpn.J.Appl.phys., volume 30, L1941 (1991)]; Polyparaphenylene [for example, Adv.Mater., volume 4, the 36 pages (1992)]; Polyarylene is polypyrrole, polypyridine, polyaniline, Polythiophene etc. for example; Poly-aryl vinylidene is poly-right-phenylene vinylidene and poly-inferior thienyl vinylidene (for example, WO 98/27136) for example; Polyphenylene sulfide, polycarbazole etc.[for example, " Advance Materialsvol.12 1737-1750 (2000) and " Organic EL Display Technology, MonthlyDisplay, December issue, P.68-73 "]
In the middle of them, preferred polyarylene type luminescence polymer.
As for the repeating unit that in polyarylene type luminescence polymer, comprises, example be arylidene and divalent heterocycle, preferred those that form by 2 to 100 moles of % of these repeating units, more preferably those that form by 50 to 99 moles of % of these repeating units.
The carbonatoms that constitutes the ring of arylidene is about 6 to 60 usually.Its specific examples comprises phenylene, biphenylene, inferior terphenyl, naphthalene two bases, anthracene two bases, luxuriant and rich with fragrance two bases, pentalene two bases, indenes two bases, heptalene two bases, indacenediyl base, triphenylenyl two bases, dinaphthalene two bases, phenylnaphthalene two bases, 1,2-toluylene two bases, fluorenes two bases (for example, the A=-C in following formula (4) (R ') (R ')-situation).
The carbonatoms that constitutes the ring of divalent heterocycle is about 3 to 60 usually.Its specific examples comprises pyridine two bases, diaza phenylene, quinoline two bases, quinoxaline two bases, acridine two bases, dipyridyl two bases, phenanthroline two bases, and in following formula (4), they be X=-O-,-S-,-Se-,-NR " ,-C (R ') (R ')-or Si (R ') (R ')-situation.
In addition, the situation that preferably comprises the repeating unit of representing by following formula (4):
(wherein, A represents to be used for forming with 4 carbon atoms on two phenyl ring of this formula the atom or the atomic group of 5 yuan of rings or 6 yuan of rings; R
4a, R
4b, R
4c, R
5a, R
5bAnd R
5cRepresent hydrogen atom independently of one another, halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, acyl group, acyloxy, amide group, the acid imide base, the imines residue, the amino that replaces, the silyl that replaces, the siloxy-that replaces, the silylthio-that replaces, the silylamino-that replaces, cyano group, nitro, the unit price heterocyclic radical, heteroaryloxy, heteroarylthio, alkoxy carbonyl, aryloxycarbonyl, aryl-alkoxy carbonyl, heteroaryloxy carbonyl or carboxyl; R
4bAnd R
4cTogether and R
5bAnd R
5cCan form ring together.)
A represents to be used for forming with 4 carbon atoms on two phenyl ring of this formula the atom or the atomic group of 5 yuan of rings or 6 yuan of rings, and its specific examples includes, but are not limited to following:
Wherein, R, R ' and R " independent respectively expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, acyloxy, the amino of replacement, the siloxy-of replacement, the silylthio-of replacement, silylamino-, cyano group, nitro or the unit price heterocyclic radical of replacement.R ' independence expression hydrogen atom, halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, acyl group, acyloxy, amide group, acid imide base, imines residue, the amino of replacement, the silyl of replacement, the siloxy-of replacement, the silylthio-of replacement, silylamino-, cyano group, nitro or the unit price heterocyclic radical of replacement.R " independent expression hydrogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, acyl group, the silyl of replacement, the siloxy-of replacement, the silylthio-of replacement, the silylamino-or the unit price heterocyclic radical of replacement.
As at R, R ' and R " in halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyl group, acyloxy and the unit price heterocyclic radical of replacement, its definition and specific examples and top R
3, R
4, R
5And R
6Those are identical.
In A, preferred-O-,-S-,-Se-,-NR " ,-CR ' R '-and SiR ' R '-, and more preferably-O-,-S-and-CR ' R '-.
At R
4a, R
4b, R
4c, R
5a, R
5b, R
5cIn halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; arylalkyl; alkoxy aryl; alkylthio-aryl; alkenyl; alkynyl; aryl alkenyl; aromatic yl polysulfide yl; acyl group; acyloxy; amide group; the acid imide base; the imines residue; the amino that replaces; the silyl that replaces; the siloxy-that replaces; the silylthio-that replaces; the silylamino-that replaces; cyano group; nitro; the unit price heterocyclic radical; heteroaryloxy; heteroarylthio; alkoxy carbonyl; aryloxycarbonyl; aryl-alkoxy carbonyl and heteroaryloxy carbonyl are identical with top those.
As for repeating unit by following formula (4) expression, example be following structure:
Wherein, the hydrogen atom on the phenyl ring can be replaced by the silylamino-of the silylthio-of the siloxy-of the silyl of the amino of halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, acyl group, acyloxy, amide group, acid imide base, imines residue, replacement, replacement, replacement, replacement, replacement, cyano group, nitro or unit price heterocyclic radical.Have two substituting groups in the consecutive position at phenyl ring, they can be connected to form ring.
Except that arylidene and divalent heterocycle, be used for luminescence polymer of the present invention and for example can also comprise repeating unit derived from aromatic amine.In this case, can provide hole injection efficiency and transportation performance.
In this case, the repeating unit of being made up of arylidene and divalent heterocycle is generally 99: 1 to 20: 80 with molar ratio derived from the repeating unit of aromatic amine.
As for repeating unit, preferably by the repeating unit of following formula (8) expression derived from aromatic amine:
Wherein, Ar
4, Ar
5, Ar
6And Ar
7Represent arylidene or divalent heterocycle independently of one another, Ar
8, Ar
9And Ar
10Represent aryl or unit price heterocyclic radical independently of one another, o and p independently represent 0 or 1 separately, and 0＜=o+p＜=2.
Here, those of the definition of arylidene or divalent heterocycle and specific examples and top T are identical.The definition of aryl or unit price heterocyclic radical and specific examples and top X
1And X
2Those are identical.
As for specific examples by the repeating unit of top formula (8) expression, example be following structure.
Wherein, the hydrogen atom on the aromatic ring can be by halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; arylalkyl; alkoxy aryl; alkylthio-aryl; alkenyl; alkynyl; aryl alkenyl; aromatic yl polysulfide yl; acyl group; acyloxy; amide group; the acid imide base; the imines residue; the amino that replaces; the silyl that replaces; the siloxy-that replaces; the silylthio-that replaces; the silylamino-that replaces; cyano group; nitro; the unit price heterocyclic radical; heteroaryloxy; heteroarylthio; alkoxy carbonyl; aryloxycarbonyl; aryl-alkoxy carbonyl; heteroaryloxy carbonyl and carboxyl replace.
In repeating unit, especially preferably by the repeating unit of following formula (9) expression by following formula (8) expression:
Wherein, R
7, R
8And R
9Independent separately expression halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; arylalkyl; alkoxy aryl; alkylthio-aryl; alkenyl; alkynyl; aryl alkenyl; aromatic yl polysulfide yl; acyl group; acyloxy; amide group; the acid imide base; the imines residue; the amino that replaces; the silyl that replaces; the siloxy-that replaces; the silylthio-that replaces; the silylamino-that replaces; cyano group; nitro; the unit price heterocyclic radical; heteroaryloxy; heteroarylthio; alkoxy carbonyl; aryloxycarbonyl; aryl-alkoxy carbonyl; heteroaryloxy carbonyl or carboxyl.X and y independently represent 0 to 4 integer separately.Z represents 0 to 2 integer.W represents 0 to 5 integer.
Be used for luminescence polymer of the present invention and can also be random, block or grafting polymers, or have the polymkeric substance of structure in the middle of it, for example, have the random copolymers of block performance.Consider the polymers copolymers that obtains having high fluorescence quantum yield, for random copolymers completely, the random copolymers, block or the graft copolymer that preferably have the block performance.In addition, can also comprise the polymkeric substance that has the branching main chain and surpass three end groups, and branch-shape polymer (dendrimer).
As for the end group that is used for luminescence polymer of the present invention, if the complete reservation of polymerizable groups in the time of in entering device, may reduce luminescent properties and work-ing life.And can with stablize radical protection they.Preferably have those of the conjugated link(age) that extend to the main chain conjugated structure, example be the structure that is connected with aryl or heterogeneous ring compound base by C-C.Particularly, example is as the 0 described substituting group of the Chemical formula 1 in JP-A-9-45478.
As for being used for luminescence polymer of the present invention, the number-average molecular weight of preferred polystyrene conversion is about 10
3To 10
8, the number-average molecular weight of preferred polystyrene conversion is about 10
4To 10
6
In addition, because use luminous from film, as for luminescence polymer, the preferred use with those of solid luminescent.
The synthetic method that is used for luminescence polymer of the present invention for example comprises: the corresponding monomer methods of polymerization by the Suzuki linked reaction; The polymerization process by Grignard reaction; The polymeric method by Ni (0) catalyzer; Use for example FeCl of oxygenant
3Deng and the polymeric method; The method of electrochemically oxidative polymerization; With the method that has the intermediate polymer of suitable leavings group by decomposition.In the middle of them, preferably pass through the Suzuki linked reaction and the corresponding monomer methods of polymerization; The polymerization process by Grignard reaction; The polymeric method by Ni (0) catalyzer is because reaction can be controlled easily.
When using luminescence polymer as the luminescent material of polymer LED, its purity exerts an influence to luminescent properties, therefore, preferably before polymerization by the monomer before the method purifying polymerization such as distillation, sublimation purification, recrystallization etc., in addition, preferably after synthetic, carry out purification process, for example redeposition purifying, chromatography etc.
Luminescent-polymer composition of the present invention comprises luminescence polymer and ion pair.Based on the luminescence polymer of 100 weight parts, the content of ion pair is generally 0.001 to 10 weight part, is preferably 0.001 to 5 weight part, 0.001 to 1 weight part more preferably, and 0.01 to 1 weight part more preferably.
In addition, luminescence polymer liquid composite of the present invention comprises luminescence polymer, ion pair and solvent.
Use this liquid composite, can form luminescent layer by coating process.Usually comprise luminescent-polymer composition of the present invention by the luminescent layer that uses this liquid composite preparation.
As for solvent, example be chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), toluene, dimethylbenzene, 1,1,2,3,4-tetralin, naphthalane, just-butylbenzene etc.
Luminescence polymer, though depend on its structure and molecular weight, in these solvents, can dissolve usually 0.1 weight % or more than.
Based on the luminescence polymer of 100 weight parts, quantity of solvent is about 1000 to 100000 weight parts usually.
As required, composition of the present invention can comprise tinting material, charge transport material etc.
Polymer LED of the present invention is included in the luminescent layer between the electrode of being made up of anode and negative electrode, and luminescent layer comprises luminescent-polymer composition of the present invention.
In addition, polymer LED of the present invention is included in the luminescent layer between the electrode of being made up of anode and negative electrode, and luminescent layer is the liquid composite formation of the application of the invention.
In addition, polymer LED of the present invention comprises: the polymer LED with the electron supplying layer between negative electrode and luminescent layer; Polymer LED with the hole transporting layer between anode and luminescent layer; And have electron supplying layer between negative electrode and luminescent layer, and has the polymer LED of the hole transporting layer between anode and luminescent layer.
Particularly, example is that following structure is a) to d):
A) anode/luminescent layer/negative electrode
B) anode/hole transporting layer/luminescent layer/negative electrode
C) anode/luminescent layer/electron supplying layer/negative electrode
D) anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode
(wherein, "/" is meant the lamination of adjacent layer.Below, identical)
Here, luminescent layer is the layer with radiative function, and hole transporting layer is the layer with the function of carrying the hole.Here, electron supplying layer and hole transporting layer are generically and collectively referred to as charge transport layer.
Can also use two-layer or more multi-layered luminescent layer, hole transporting layer and electron supplying layer independently of one another.
Usually, the charge transport layer that claims adjacent electrode to settle sometimes especially is electric charge injection layer (hole injection layer, an electron injecting layer), and described electric charge injection layer has the function of the electric charge injection efficiency of improving self-electrode and has the effect that reduces device drive voltage.
In order to improve with the bounding force of electrode and to improve the electric charge that comes self-electrode and inject, can also provide above-mentioned electric charge injection layer or thickness at adjacent electrode is 2nm or following insulation layer, in addition, for the bounding force that improves the interface, prevent to mix etc., can also will approach in the interface that buffer layer is inserted into charge transport layer and luminescent layer.
In the luminosity factor of considering device with in work-ing life, can suitably use the order and the quantity of laminated layer of institute, and every layer thickness.
In the present invention, as for the polymer LED with electric charge injection layer (electron injecting layer, hole injection layer) that is provided, that list is the polymkeric substance ELD that the polymer LED of the electric charge injection layer that provides in the negative electrode vicinity is provided and the electric charge injection layer that provides at contiguous anode is provided.
For example, that special example is following structure e) to p):
E) anode/electric charge injection layer/luminescent layer/negative electrode
F) anode/luminescent layer/electric charge injection layer/negative electrode
G) anode/electric charge injection layer/luminescent layer/electric charge injection layer/negative electrode
H) anode/electric charge injection layer/hole transporting layer/luminescent layer/negative electrode
I) anode/hole transporting layer/luminescent layer/electric charge injection layer/negative electrode
J) anode/electric charge injection layer/hole transporting layer/luminescent layer/electric charge injection layer/negative electrode
K) anode/electric charge injection layer/luminescent layer/electron supplying layer/negative electrode
L) anode/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode
M) anode/electric charge injection layer/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode
N) anode/electric charge injection layer/hole transporting layer/luminescent layer/electron supplying layer/negative electrode
O) anode/hole transporting layer/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode
P) anode/electric charge injection layer/hole transporting layer/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode
Specific examples as for electric charge injection layer, example be the layer that comprises conductive polymers, be placed between anode and the hole transporting layer and comprise the layer of ionization potential at the ionization potential of anode material and the material between the ionization potential of the hole transporting material that hole transporting layer comprises, be placed between negative electrode and the electron supplying layer and comprise and have affinity electric at the electron affinity of cathode material and the layer of the material between the electron affinity of the electron transport materials that electron supplying layer comprises, etc.
When above-mentioned electric charge injection layer is that the electric conductivity of preferred conductive polymers is 10 when comprising the layer of conductive polymers
-5S/cm or above and 10
3S/cm or following, and for the electric current that reduces between the light emitting pixel leaks, more preferably 10
-5S/cm or above and 10
2S/cm or following, more preferably 10
-5S/cm or above and 10
1S/cm or following.
Usually, be 10 for electric conductivity is provided
-5S/cm or above and 10
3S/cm or following conductive polymers, the ion of doping sufficient quantity in conductive polymers.
As for the kind of doping electronics, in hole injection layer, use negatively charged ion and in electron injecting layer, use positively charged ion.As for anionic example, example be polystyrolsulfon acid radical ion, benzene sulfonamide acid ion, camphorsulfonic acid radical ion etc., and as for cationic example, example be lithium ion, sodium ion, potassium ion, TBuA ion etc.
The thickness of electric charge injection layer is preferably 2nm to 50nm for for example 1nm to 100nm.
Consider the relation of electrode materials and adjacent layer, can suitably be chosen in the material that uses in the electric charge injection layer, example be conductive polymers, for example polyaniline and derivative thereof, Polythiophene and derivative thereof, polypyrrole and derivative thereof, poly-(phenylene vinylidene) and derivative thereof, poly-(inferior thienyl vinylidene) and derivative, poly quinoline and derivative thereof, polyquinoxaline and derivative thereof, the polymkeric substance etc. that in its main chain or side chain, comprises aromatic amine and metal phthalocyanine (copper phthalocyanine etc.), carbon etc.
Thickness is that 2nm or following insulation layer have the easy function of the electric charge of making injection.As for the material of above-mentioned insulation layer, what list is metal fluoride, metal oxide, organic insulation etc.As for having the polymer LED that thickness is 2nm or following insulation layer, that lists is that the thickness that provides at adjacent cathodes is provided is the polymer LED of 2nm or following insulation layer and the polymer LED that the thickness that provides at contiguous anode is 2nm or following insulation layer is provided.
Particularly, for example, that list is the q of following structure) to ab):
Q) anode/thickness is 2nm or following insulation layer/luminescent layer/negative electrode
R) anode/luminescent layer/thickness is 2nm or following insulation layer/negative electrode
S) anode/thickness is that 2nm or following insulation layer/luminescent layer/thickness are 2nm or following insulation layer/negative electrode
T) anode/thickness is 2nm or following insulation layer/hole transporting layer/luminescent layer/negative electrode
U) anode/hole transporting layer/luminescent layer/thickness is 2nm or following insulation layer/negative electrode
V) anode/thickness is that 2nm or following insulation layer/hole transporting layer/luminescent layer/thickness are 2nm or following insulation layer/negative electrode
W) anode/thickness is 2nm or following insulation layer/luminescent layer/electron supplying layer/negative electrode
X) anode/luminescent layer/electron supplying layer/thickness is 2nm or following insulation layer/negative electrode
Y) anode/thickness is that 2nm or following insulation layer/luminescent layer/electron supplying layer/thickness are 2nm or following insulation layer/negative electrode
Z) anode/thickness is 2nm or following insulation layer/hole transporting layer/luminescent layer/electron supplying layer/negative electrode
Aa) anode/hole transporting layer/luminescent layer/electron supplying layer/thickness is 2nm or following insulation layer/negative electrode
Ab) anode/thickness is that 2nm or following insulation layer/hole transporting layer/luminescent layer/electron supplying layer/thickness are 2nm or following insulation layer/negative electrode
When the preparation luminescent layer, when forming film when this luminescence polymer liquid composite of the application of the invention and by solution, behind this solution of coating, only need by the dry solvent of removing, even and under charge transport material and luminescent material blended situation, also can adopt identical method, thus great advantage in causing producing.As for by the film forming method of solution shape, can use coating process, for example rotating coating, casting method, miniature intaglio printing coating process, intaglio printing coating process, excellent coating process, roller coat cloth method, line rod coating process, dip coated method, injection coating process, silk screen coating process, aniline (flexo) printing process, offset printing method, ink jet printing method etc.
When the preparation polymer LED, when this ligand compound compositions of the application of the invention or polymer complex compound form film by solution, behind this solution of coating, only need by the dry solvent of removing, even and under charge transport material and luminescent material blended situation, also can adopt identical method, thus great advantage in causing producing.As for by the film forming method of solution shape, can use coating process, for example rotating coating, casting method, miniature intaglio printing coating process, intaglio printing coating process, excellent coating process, roller coat cloth method, line rod coating process, dip coated method, injection coating process, silk screen coating process, aniline (flexo) printing process, offset printing method, ink jet printing method etc.
As for the thickness of luminescent layer, optimum value is according to the material that uses and difference, and can select suitably to make that driving voltage and luminous efficiency become optimum value.For example, it is 1nm to 1 μ m, is preferably 2nm to 500nm, more preferably 5nm to 200nm.
In polymer LED of the present invention, in luminescent layer, can also mix the luminescent material of the luminescence polymer above being different from.The luminescent layer that can also comprise in addition, the luminescent material that is different from top luminescence polymer with the luminescent layer lamination that comprises luminescence polymer recited above.
As for luminescent material, can use known material.In low-molecular-weight compound, can use for example naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof; Dyestuff is polymethine dyestuff, xanthene dye, coumarine dye, cyanine dyes for example; The metal complexes of oxine or derivatives thereof, aromatic amine, tetraphenyl pentamethylene or derivatives thereof, tetraphenylbutadiene or derivatives thereof etc.
Particularly, for example, can use compound known, for example JP-A 57-51781,59-195393 etc. described those.
When polymer LED of the present invention has hole transporting layer, as for the hole transporting material that uses, example be polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, contain polyorganosiloxane ramification, pyrazoline derivative, the aryl amine derivatives, 1 of aromatic amine side chain or main chain master, 2-diphenyl ethylene derivatives, triphenyl diamine derivative, polyaniline or derivatives thereof, Polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly-(right-phenylene vinylidene) or derivatives thereof, poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof etc.
The specific examples of hole transporting material is included in those described in JP-A 63-70257,63-175860,2-135359,2-135361,2-209988,3-37992 and the 3-152184.
In the middle of them, as for the hole transporting material that uses in the hole transporting layer, the preferred polymers hole transporting material, polyvinyl carbazole or derivatives thereof for example, the polysilane or derivatives thereof, the polyorganosiloxane ramification that contains aromatic amine side chain or main chain master, the polyaniline or derivatives thereof, the Polythiophene or derivatives thereof, poly-(right-phenylene vinylidene) or derivatives thereof, poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof etc., and polyvinyl carbazole or derivatives thereof more preferably, polysilane or derivatives thereof and contain the polyorganosiloxane ramification of aromatic amine side chain or main chain master.Under the situation of low-molecular-weight hole transporting material, preferably in polymer binder, disperse to use.
For example, cationoid polymerisation or radical polymerization by by vinyl monomer obtain the polyvinyl carbazole or derivatives thereof.
As for the polysilane or derivatives thereof, example be to be described in Chem.Rev.,
89, 1359 (1989) and the specification sheets announced of GB 2300196 described in compound, etc.As for synthetic, can use the method for in them, describing, and can use the Kipping method aptly especially.
As for the polysiloxane or derivatives thereof, example be to have those of the above-mentioned structure that contains the lower molecular weight hole transporting material side chain or main chain master because the cavity conveying poor performance of siloxane backbone structure.Especially, example be in side chain or main chain, to have those of aromatic amine, described aromatic amine has the cavity conveying performance.
Do not limit the method that forms hole transporting layer, and under the situation of lower molecular weight hole transporting layer, example be by the cambial method of the mixing solutions that contains polymer binder, and under the situation of polymkeric substance hole transporting layer, example be by the cambial method of solution.
Restriction is not used for by the film forming solvent of solution shape especially, as long as it can dissolve hole transporting material.As for solvent, example be for example chloroform, methylene dichloride, ethylene dichloride etc. of chlorine solvent, ether solvents is tetrahydrofuran (THF) etc. for example, aromatic hydrocarbon solvents is toluene, dimethylbenzene etc. for example, ketone solvent is for example ethyl acetate, ethyl butyrate, ethyl cellosolve acetate etc. of acetone, methyl ethyl ketone etc. and ester solvent for example.
As for by the film forming method of solution shape, can use by the coating process of solution for example rotating coating, casting method, miniature intaglio printing coating process, intaglio printing coating process, excellent coating process, roller coat cloth method, line rod coating process, dip coated method, spray coating process, silk screen printing coating process, flexographic printing method, offset printing method, ink jet printing method etc.
The preferred blended polymer binder that uses not serious interference charge transport aptly and visible light is not had strong absorption.As for this polymer binder, example be polycarbonate, polyacrylic ester, poly-(methyl acrylate), poly-(methyl methacrylate), polystyrene, poly-(vinylchlorid), polysiloxane etc.
Thickness as for hole transporting layer, optimum value is according to the material that uses and different and can suitably select to make driving voltage and luminosity factor to become optimum value, and necessary be the thickness that does not produce pin hole at least, too thick thickness is not preferred, because device drive voltage improves.Therefore, the thickness of hole transporting layer is preferably 2nm to 500nm, more preferably 5nm to 200nm for for example 1nm to 1 μ m.
When polymer LED of the present invention has electron supplying layer, use compound known as electron transport materials, example De Shi oxadiazole derivative, anthraquinone bismethane (anthraquinodimethane) or derivatives thereof, the benzoquinones or derivatives thereof, the naphthoquinones or derivatives thereof, the anthraquinone or derivatives thereof, four cyano anthraquinone bismethane or derivatives thereof, fluorenone derivatives, phenylbenzene dicyano ethene or derivatives thereof, phenoquinone, or oxine or derivatives thereof, poly quinoline and derivative thereof, polyquinoxaline and derivative thereof, the metal complexes of poly-fluorenes or derivatives thereof etc.
Particularly, example is at described in JP-A 63-70257,63-175860,2-135359,2-135361,2-209988,3-37992 and the 3-152184 those.
You Xuan oxadiazole derivative, benzoquinones or derivatives thereof, anthraquinone or derivatives thereof in the middle of them, or the metal complexes of oxine or derivatives thereof, poly quinoline and derivative thereof, polyquinoxaline and derivative thereof, poly-fluorenes or derivatives thereof etc., and 2-(4-xenyl)-5-(4-tert-butyl phenyl)-1 more preferably, 3,4-oxadiazole, benzoquinones, anthraquinone, three (8-quinolinol) aluminium and poly quinoline.
Do not limit the method that forms electron supplying layer especially, and respectively, under the situation of lower molecular weight electron transport materials, example be by the method for the vapour deposition of powder or by solution or the film forming method of melted state shape, and carry in polymer-electronics under the situation of material, example be to form membrane method by solution or melted state.
Restriction is not used for by the film forming solvent of solution shape especially, as long as it can dissolve electron transport materials and/or polymer binder.As for solvent, example be for example chloroform, methylene dichloride, ethylene dichloride etc. of chlorine solvent, ether solvents is tetrahydrofuran (THF) etc. for example, aromatic hydrocarbon solvents is toluene, dimethylbenzene etc. for example, ketone solvent is acetone, methyl ethyl ketone etc. for example, and ester solvent is ethyl acetate, ethyl butyrate, ethyl cellosolve acetate etc. for example.
As for by solution or the film forming method of melted state shape, can use coating process for example rotating coating, casting process, miniature intaglio printing coating process, intaglio printing coating process, excellent coating process, roller coat cloth method, line rod coating process, dip coated method, injection coating process, silk screen printing coating process, flexographic printing method, offset printing method, ink jet printing method etc.
The preferred blended polymer binder that uses not serious interference charge transport suitablely and visible light is not had strong absorption.As for this polymer binder, example be poly-(N-vinylcarbazole), polyaniline or derivatives thereof, Polythiophene or derivatives thereof, poly-(right-phenylene vinylidene) or derivatives thereof, poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof, polycarbonate, polyacrylic ester, poly-(methyl acrylate), poly-(methyl methacrylate), polystyrene, poly-(vinylchlorid), polysiloxane etc.
Thickness as for electron supplying layer, and different and can suitably select to make driving voltage and luminosity factor to become optimum value, necessary be the thickness that does not produce pin hole at least to optimum value according to the material that uses, and too thick thickness is not preferred, because device drive voltage improves.Therefore, the thickness of electron supplying layer is preferably 2nm to 500nm, more preferably 5nm to 200nm for for example 1nm to 1 μ m.
The base material that is preferably formed polymer LED of the present invention can be an indeclinable base material in forming electrode and organic material layer, example be glass, plastics, polymeric film, silicon substrate etc.Under the situation of opaque base material, preferred electrode of opposite is transparent or translucent.
In the electrode of being made up of anode and negative electrode at least one is transparent or translucent.Preferred anodes is transparent or translucent.
As for this anodic material, use be conducting metal oxide film, semi-transparent metals film etc.Particularly, use be Indium sesquioxide, zinc oxide, stannic oxide and composition thereof, that is, and indium/tin/oxide compound (ITO) and by using film (NESA etc.) that the conductive glass be made up of indium/tin/oxide compound makes etc. and gold, platinum, silver, copper etc.In the middle of them, preferred ITO, indium/tin/oxide compound, stannic oxide.As for manufacture method, use be vacuum vapor deposition method, sputtering method, ion plating method, electro-plating method etc.As for anode, can also use organic nesa coating, for example polyaniline or derivatives thereof, Polythiophene or derivatives thereof etc.
In the transmission and electric conductivity of considering light, can suitably select anodic thickness, for example be 10nm to 10 μ m, be preferably 20nm to 1 μ m, more preferably 50nm to 500nm.
In addition,, can on anode, provide the layer that comprises phthalocyanine derivates conductive polymers, carbon etc., or mean thickness is 2nm or the following layer that comprises metal oxide, metal fluoride, organic insulation etc. etc. for electric charge injects easily.
As for the cathode material that uses in the polymer LED of the present invention, preferably has the material of low work content.For example, use metal, for example lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, aluminium, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium etc., or comprise two or more alloys in them, or comprise one or more alloy of one or more and gold and silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin in them, graphite or graphite lamellar compound etc.The example of alloy comprises magnesium-silver alloys, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloys, lithium-aluminium alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminium alloy etc.Negative electrode can form two-layer or the multiwalled laminar structure.
In the transmission and electric conductivity of considering light, can suitably select the thickness of negative electrode, for example be 10nm to 10 μ m, be preferably 20nm to 1 μ m, more preferably 50nm to 500nm.
As for the method for making negative electrode, use be vacuum vapor deposition method, sputtering method and wherein at the laminating method of time bonding metal film such as heat and pressure.In addition; the layer that comprises conductive polymers can also be provided between negative electrode and organic layer; or mean thickness is 2nm or the following layer that comprises metal oxide, metal fluoride, organic insulation etc., and after making negative electrode, can also provide the protective layer of protection polymer LED.Use polymer LED for long-term stability, preferably provide protective layer and/or protective cover with protection device, purpose is to prevent destruction from the outside.
As for protective layer, can use polymerizable compound, metal oxide, metal fluoride, metal borate etc.As for protective cover, can use sheet glass, plastic sheet, water osmotic treated etc. has been hanged down on its surface, and can suitably use wherein will be covered with device substrate by thermosetting resin that seals usefulness or light-cured resin and paste the method that is attached to.If use dividing plate to keep the space, prevent that easily device is damaged.If, can prevent the oxidation of negative electrode, in addition,, can easily suppress the device failure that causes by adherent moisture in process of production by place for example barium oxide etc. of siccative in above-mentioned space at this space sealing rare gas element for example nitrogen and argon.In the middle of them, preferably adopt one or more methods.
In device of the present invention, consider the work-ing life of device, preferably during forming luminescent layer or afterwards, the device for preparing by thermal treatment under 50 ℃ or above temperature.
Heat treated condition is the salt condition of decomposing by thermal treatment normally.Thermal treatment temp be 50 ℃ or more than, preferably it is in 50 ℃ to 300 ℃ scope.Heat treatment time is generally about 1 second to 24 hours.
Can use that for example hot plate, baking oven, infrared(ray)lamp etc. are heat-treated.Can under reduced pressure heat-treat.
As for thermal treatment, preferably it carries out after forming luminescent layer, more preferably carries out immediately after forming luminescent layer.
In addition, device of the present invention can or expose by irradiation afterwards during forming luminescent layer and prepare.As for irradiation, example be for example ultraviolet ray, electron beam and X-ray, preferred ultraviolet ray.
Polymer LED of the present invention can be used for flat-plate light source, segment displays, dot-matrix display and liquid-crystal display as backlight, etc.
In order to use polymer LED of the present invention to obtain the luminous of plane form, can suitably place anode and negative electrode with plane form, make their mutual laminations.In addition, in order to obtain the luminous of pattern form, a kind of method is to place the mask of the window with pattern formation on above-mentioned zero diopter luminescent device, a kind of method is to form organic layer to obtain providing non-luminous substantially very thick thickness in non-luminous component, a kind of method is to form any in the male or female in pattern, or in them two kinds.Form patterns by any in these methods with by placing some electrodes, making can independent ON/OFF, obtains the sectional type display device, and it can display digit, letter, simple marking etc.In addition, in order to form dot-matrix display, anode and negative electrode are made bar form and placed may be favourable, makes their crossing at right angle.By the method for the polymerizable compound of the multiple light that sends different colours placed apart wherein, or wherein use the method for color filter or luminescent conversion spectral filter, obtain background colour indicating meter (area color display) and broken colour indicating meter.Dot-matrix display can be by passive driving, or waits by the active drive with the TFT combination and to drive.Can use the indicating meter of these display devices as view finder of computer, televisor, portable terminal device, Cell phone, auto navigation, Kamera etc.In addition, the luminescent device of above-mentioned plane form is to approach self luminescent device, and the zero diopter source that can suitably use as backlight liquid crystal display, or as luminous zero diopter source.In addition, if use flexible sheet, it can also be as crooked light source or indicating meter.
Below, in order at length to explain the present invention, with reference to shown in embodiment, but the present invention is not subjected to the restriction of these embodiment.
Here, as for number-average molecular weight, the number-average molecular weight of polystyrene conversion uses chloroform or tetrahydrofuran (THF) to obtain as solvent by gel permeation chromatography (GPC).
Synthetic embodiment 1 (synthesizing of compd A)
With the inside of the eggplant type flask of nitrogen replacement 300ml, three (pentafluorophenyl group) borine of dissolving 5.00g in the dehydration diethyl ether of 200ml, and add the potassium cyanide of 0.31g.After refluxing 3 hours, distill solvent, and obtain the compd A of 5.71g.
MS (ESI-is negative)
m/z 1049.8([M-K]
-)
Embodiment 2 (synthesizing of compd B)
With the inside of the Schlenk test tube of nitrogen replacement 25ml, in the water of 4.0ml, dissolve 1,1 '-dimethyl-4,4 '-dipyridyl dichloride 40mg, and add compd A 400mg.Add the chloroform of 4.0mml, and stirred 4.5 hours.After filtering and washing, distill solvent, obtain the compd B of 288mg.
1H-NMR(300MHz，DMSO-d
6)
δ9.30(4H，brs)，8.78(4H，brs)，4.47(6H，s)
Embodiment 3 (synthesizing of Compound C)
With the inside of the Schlenk test tube of nitrogen replacement 25ml, two (4-tert-butyl phenyl) iodine trifluoromethyl sulfonic acid (triflate) 150mg suspends in the water of 4.0ml.Add compd A 392mg, add toluene 3ml again, insoluble then material is dissolved.After stirring 8 hours, carry out layering, and use the toluene aqueous phase extracted.After with dried over sodium sulfate, distill solvent, obtain the Compound C of 373mg.
1H-NMR(DMSO-d
6，300MHz)
δ8.16(4H，d)，7.55(H，m)，1.26(18H，s)
δ-132.5，-133.6，-134.1，-157.8，-159.7，-164.1，-165.2
Synthetic embodiment 4 (synthesizing of Compound D)
With the inside of the Schlenk test tube of nitrogen replacement 25ml, dissolving triphenylsulfonium bromide 100mg in the water of 4.0ml.When adding compd A 408mg, solution becomes gets muddy.Add 3ml toluene and stir after 8 hours, carry out layering and with toluene and diethyl ether aqueous phase extracted.After with dried over sodium sulfate, distill solvent, obtain the Compound D of 449mg.
1H-NMR(DMSO-d
6，300MHz)
δ7.90-7.75(15H，m)
19F-NMR(DMSO-d
6，300MHz)
δ-132.7，-133.7，-134.1，-157.9，-160.0，-164.2，-165.3
Synthetic embodiment 5
Synthesizing of＜luminescence polymer 1 〉
In the dehydration tetrahydrofuran (THF) of 1600mL, dissolving 2,7-two bromo-9,9-dioctyl fluorene (26g, 0.047mol), 2,7-two bromo-9,9-diisoamyl fluorenes (5.6g, 0.012mol) and 2, (22g 0.41mol), replaces the inside of this system to 2 '-dipyridyl by nitrogen bubble.Under nitrogen atmosphere, in this solution, add two (1, the 5-cyclooctadiene) Ni (0) { Ni (COD)
2(40g 0.15mol), is elevated to 60 ℃ and reacted 8 hours with temperature.After reaction, with reaction mixture cool to room temperature (about 25 ℃), be added drop-wise in the mixing solutions of 25% ammoniacal liquor 200ml/ methyl alcohol 1200mL/ ion exchanged water 1200mL, and stir about 30 minutes.The settling of filtering-depositing, and dry air.In toluene 1100mL, after the dissolving, filter it, filtering solution is added drop-wise among the methyl alcohol 3300mL, and stirred 30 minutes.The settling of filtering-depositing, and with methyl alcohol 1000mL washing, drying under reduced pressure is 5 hours then.The output of the multipolymer that obtains is 20g (hereinafter referred to as luminescence polymer 1).The number-average molecular weight and the weight-average molecular weight of the polystyrene conversion of luminescence polymer 1 are respectively Mn=9.9 * 10
4And Mw=2.0 * 10
5, (mobile phase: chloroform).
Synthetic embodiment 6
＜4-tert-butyl-2,6-dimethyl bromobenzene synthetic 〉
Under inert atmosphere, the acetate of the 225g that in the three-necked flask of 500ml, packs into, and the 5-tert-butyl of adding 24.3g--dimethylbenzene.Then, behind the bromine that adds 31.2g, under 15 to 20 ℃, reacted 3 hours.
In the water of 500ml, add reaction liquid, the settling of filtering-depositing.With the water washing twice of 250ml, obtain the white solid of 34.2g.
1H-NMR(300MHz/CDCl
3)：
δ(ppm)＝1.3[s，9H]，2.4[s，6H]，7.1[s，2H]
MS(FD
+)M
+241
Synthetic embodiment 7
＜N, N '-phenylbenzene-N, N '-two (4-tert-butyl-2,6-3,5-dimethylphenyl)-1,4-phenylenediamine synthetic 〉
Under inert atmosphere, in the three-necked flask of 100ml, the toluene 36ml of pack into the degassing and dehydration.Then, add three (tert-butyl) phosphine of 0.63g, three (dibenzalacetone (dibenzylidineacetone)), two palladiums of 0.41g, the top 4-tert-butyl-2 of 9.6g, uncle-the sodium butylate of 6-dimethyl bromobenzene, 5.2g and the N of 4.7g, N '-phenylbenzene-1, the 4-phenylenediamine, and 100 ℃ of reactions 3 hours.
In the saturated NaCl aqueous solution of 300ml, add reaction liquid, by extracting at about 50 ℃ of warm chloroform 300ml.After solvent evaporated, add toluene 100ml, and heating is dissolved up to solid.After placing cooling, the filter deposition thing obtains the white solid of 9.9g.
Synthetic embodiment 8
＜N, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-2,6-3,5-dimethylphenyl)-1,4-phenylenediamine synthetic 〉
Under inert atmosphere, the N that in the three-necked flask of 1000ml, packs into and dewater, dinethylformamide 350ml, and the N of dissolving 5.2g, N '-phenylbenzene-N, N '-two (4-tert-butyl-2,6-3,5-dimethylphenyl)-1, the 4-phenylenediamine, drip the succinimide of 3.5g/and N then, dinethylformamide solution, under ice bath refrigerative condition, reaction is carried out a whole day and a whole night.
The water that adds 150ml in reaction liquid, the settling of filtering-depositing with its methanol wash twice with 50ml, obtains the white solid of 4.4g.
1H-NMR(300MHz/THF-d8)：
δ (ppm)=1.3[s, 18H], 2.0[s, 12H] and, 6.6 to 6.7[d, 4H], 6.8 to 6.9[br, 4H] and, 7.1[s, 4H], 7.2 to 7.3[d, 4H]
MS(FD
+)M
+738
Synthetic embodiment 9
Synthesizing of＜luminescence polymer 2 〉
In tetrahydrofuran (THF) 420ml, 2 above the dissolving, 7-two bromo-3,6-two octyloxy dibenzothiophene (5.4g, 9mmol, synthetic), top N according to JP-A-2004-002703, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-2,6-3,5-dimethylphenyl)-1,4-phenylenediamine (4.5g, 6mmol) with 2, and 2 '-dipyridyl (5.1g, 33mmol), and use nitrogen bubble, replace the inside of this system.Under nitrogen atmosphere, in this solution, add two (1, the 5-cyclooctadiene) Ni (0) { Ni (COD)
2(9.0g 33mmol), is elevated to 60 ℃ with temperature, under agitation reacts 3 hours.After the reaction,, be added drop-wise in the mixing solutions of 25% ammoniacal liquor 150ml/ methyl alcohol 1500mL/ ion exchanged water 600mL, stirred 1 hour reaction mixture cool to room temperature (about 25 ℃).The settling of filtering-depositing, drying under reduced pressure 2 hours is dissolved among the toluene 450mL then.Then, add the hydrochloric acid 450mL of 1N, stir about 1 hour is removed water layer, adds 4% ammoniacal liquor 450mL in organic layer, and after stirring 1 hour, removes water layer.In methyl alcohol 1350mL, drip organic layer, stirred 1 hour, the settling of filtering-depositing, drying under reduced pressure 2 hours, and be dissolved among the toluene 400mL.Then, carry out purifying, in methyl alcohol 1350mL, drip the toluene solution of collecting, stirred the settling of filtering-depositing, drying under reduced pressure 2 hours 1 hour by alumina column (amount of aluminum oxide is 100g).
The output of the multipolymer that obtains is 5.5g (hereinafter referred to as luminescence polymer 2).The number-average molecular weight and the weight-average molecular weight of polystyrene conversion are respectively Mn=3.0 * 10
4And Mw=1.8 * 10
5, (mobile phase: chloroform).
Synthetic embodiment 10 (synthesizing of Compound P)
Compound P
Under inert atmosphere, in the three-necked flask of 300ml, add 1-naphthalene boronic acids 5.00g (29mmol), 2-bromobenzaldehyde 6.46g (35mmol), salt of wormwood 10.0g (73mmol), toluene 36ml and ion exchanged water 36ml, at room temperature under agitation carried out the argon gas bubbling 20 minutes.Then, add four (triphenylphosphine) Pd 16.8mg (0.15mmol), at room temperature stir again and carried out the argon gas bubbling 10 minutes.Temperature is elevated to 100 ℃, reacted 25 hours.After being cooled to room temperature, extract organic layer with toluene, use dried over sodium sulfate, distill solvent then.By using toluene: the mixed solvent of hexanaphthene=1: 2 by the silicagel column purifying, obtains the compound of 5.18g (productive rate is 86%) as elutriant, is white crystal.
1H-NMR(300MHz/CDCl
3)：
δ7.39-7.62(m，5H)，7.7(m，2H)，7.94(d，2H)，8.12(dd，2H)，9.63(s，1H)
MS(APCI(+))：(M+H)
+233
Synthetic embodiment 11
(synthesizing of compound Q)
Compound Q
Under inert atmosphere, in the three-necked flask of 300ml, the Compound P of the 8.00g that packs into (34.4mmol) and the THF 46ml of dehydration are cooled to it-78 ℃.Then, will be just-octyl group magnesium bromide (1.0mol/1THF solution) 52ml dripped 30 minutes.After dropping, temperature is elevated to 0 ℃, stir after 1 hour, temperature is elevated to room temperature, and stirred 45 minutes.In ice bath, termination reaction is used the ethyl acetate extraction organic layer by the 1N hydrochloric acid that adds 20mL, uses dried over sodium sulfate.
After the solvent evaporated, by using toluene: the mixed solvent of hexane=10: 1 by the silicagel column purifying, obtains the compound Q of 7.64g (productive rate is 64%) as elutriant, is light yellow oil.Observe two peaks by the HPLC measurement, but these are identical with the total mass number of measuring by LC-MS, and it is regarded as isomer mixture.
Synthetic embodiment 12
(synthesizing of compound R)
Compound R
Under inert atmosphere, in the three-necked flask of 500ml, add compound Q (isomer mixture) and the dehydration methylene dichloride of 74ml, the at room temperature stirring and dissolving of 5.00g (14.4mmol).Then, at room temperature, dripped etherate of trifluoroboron 1 hour, after the adding, indoor stirring 4 hours.Stir down, slowly add ethanol 125ml, after heat produces termination, use the chloroform extraction organic layer, wash twice with water, use dried over mgso.
Behind the solvent that evaporates,, obtain the compound R of 3.22g (productive rate is 68%), be water white oil by passing through the silicagel column purifying as elutriant with hexane solvent.
1H-NMR(300MHz/CDCl
3)：
δ 0.90 (t, 3H), 1.03 to 1.26 (m, 14H) and 2.13 (m--) 2H, 4.05 (t, 1H), 7.35 (dd, 1H), 7.46 to 7.50 (m, 2H), 7.59 to 7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H), 8.75 (d, 1H)
MS(APCI(+))：(M+H)
+329
Synthetic embodiment 13
(synthetics S's is synthetic)
Compound S
Under inert atmosphere, in the three-necked flask of 200ml, the ion exchanged water of the 20ml that packs into stirs down, adds the sodium hydroxide of 18.9g (0.47mols) in proportion, and dissolving.After solution is cooled to room temperature, add toluene 20ml, the compound R of 5.17g (15.7mmol) and the bromination tributyl ammonium of 1.52g (4.72mmol), temperature is elevated to 50 ℃, just dripping-n-octyl bromide, after dropping, in 50 ℃ of reactions 9 hours.After the reaction, extract organic layer, wash twice with water, pass through dried over sodium sulfate with toluene.By using hexane solvent as elutriant, by the silicagel column purifying, obtain the compound S of 5.13g (productive rate is 74%), be yellow oil.
1H-NMR(300MHz/CDCl
3)：
δ 0.52 (m, 2H), 0.79 (t, 6H) and 1.00 to 1.20 (m--) 22H, 2.05 (t, 4H), 7.34 (d, 1H), 7.40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8.75 (d, 1H)
MS(APCI(+))：(M+H)
+441
Synthetic embodiment 14
(compound T's is synthetic)
Compound T
Under air atmosphere, in the three-necked flask of 50ml, the compound S of the 4.00g that packs into (9.08mmol), and acetate: the mixed solvent 57ml of methylene dichloride=1: 1, at room temperature stirring and dissolving.Then, stir adding three bromobenzyls-trimethyl ammonium 7.79g (20.0mmol) down, and the adding zinc chloride dissolves fully up to three bromobenzyls-trimethyl ammonium.After at room temperature stirring 20 hours, termination reaction is used the chloroform extraction organic layer by 5% the aqueous solution of sodium bisulfite that adds 10ml, uses the wet chemical washed twice, uses dried over sodium sulfate.
By with hexane as elutriant by behind quick post (flash column) purifying, pass through ethanol: hexane=1: 1, ethanol then: the mixed solvent recrystallization of hexane=10: 1, obtain the compound T of 4.13g (productive rate is 76%), be white crystal.
1H-NMR(300MHz/CDCl
3)：
δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01 to 1.38 (m, 22H), 2.09 (t, 4H), 7.62 to 7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS(APPI(+))：(M+H)
+598
Synthetic embodiment 15
Synthesizing of＜luminescence polymer 3 〉
Dissolved compound T (8.0g) and 2 in tetrahydrofuran (THF) 300mL is behind 2 '-dipyridyl (5.9g), by nitrogen bubble, by the inside of this system of nitrogen replacement.Under nitrogen atmosphere, solution is elevated to 60 ℃, add two (1, the 5-cyclooctadiene) Ni (0) { Ni (COD)
2(10.4g is 0.038mol) with reaction 5 hours.After the reaction, with reaction liquid cool to room temperature (about 25 ℃), be added drop-wise in the mixing solutions of 25% ammoniacal liquor 40ml/ methyl alcohol 300mL/ ion exchanged water 300mL, stir about is after 30 minutes, the sedimentary settling of dry air.Then, in toluene 400mL, after the dissolving, filter it, filtering solution is passed through the alumina column purifying.Add the 1N hydrochloric acid of about 300mL, stirred 3 hours, remove water layer, 4% of the about 300mL of adding ammoniacal liquor in organic layer is removed water layer after stirring 2 hours then.After in organic layer, adding the ion exchanged water of about 300mL and stirring 1 hour, remove water layer.Methyl alcohol drip about 100mL in organic layer stirred 1 hour and placed, and removed supernatant layer liquid by decant.The settling that obtains is dissolved among the toluene 200mL, and it is dropped in the methyl alcohol of about 200mL, stirred 1 hour, filter drying under reduced pressure 2 hours.The output of the multipolymer that obtains is 4.1g (below, be called luminescence polymer 3).The number-average molecular weight and the weight-average molecular weight of the polystyrene conversion of luminescence polymer 3 are respectively Mn=1.5 * 10
5And Mw=2.7 * 10
5, (mobile phase: tetrahydrofuran (THF)).
Synthetic embodiment 16
Synthesizing of＜luminescence polymer 4 〉
Dissolved compound T (0.65g) and N in tetrahydrofuran (THF) 100mL, N '-two (4-bromophenyl)-N, N '-two (4-tert-butyl-2, the 6-3,5-dimethylphenyl)-1,4-phenylenediamine (0.4g) and 2 is behind 2 '-dipyridyl (0.58g), by nitrogen bubble, by the inside of this system of nitrogen replacement.Under nitrogen atmosphere, add two (1, the 5-cyclooctadiene) Ni (0) { Ni (COD)
2(10.4g 0.038mol), is elevated to 60 ℃ with temperature, stirring reaction 3 hours.After the reaction, with reaction liquid cool to room temperature (about 25 ℃), be added drop-wise in the mixing solutions of 25% ammoniacal liquor 10ml/ methyl alcohol 100mL/ ion exchanged water 100mL, stir about is after 1 hour, the sedimentary settling of drying under reduced pressure 6 hours.Then, after being dissolved in toluene 50mL, filter it, and filtering solution is passed through the alumina column purifying.Add the ammoniacal liquor of about 50mL, stirred 2 hours, remove water layer.After in organic layer, adding the ion exchanged water of about 50mL and stirring 1 hour, remove water layer.After in organic layer, dripping the methyl alcohol of about 100mL, stirred 1 hour and placed, remove supernatant layer liquid by decant.Dissolve the settling that obtains in toluene 50mL, and it is dropped in the methyl alcohol of about 200mL, stir about 1 hour filters drying under reduced pressure 2 hours.The output of the multipolymer that obtains is 390mg (below, be called luminescence polymer 4).The number-average molecular weight and the weight-average molecular weight of the polystyrene conversion of luminescence polymer 4 are respectively Mn=1.6 * 10
4And Mw=7.4 * 10
4, (mobile phase: tetrahydrofuran (THF)).
Synthetic embodiment 17 (synthesizing of compd E)
With the inside of the four neck flasks of nitrogen replacement 200ml, three (4-tert-butyl phenyl sulfonium) trifluoro-methanyl sulfonate, compd A 0.873g, ion exchanged water 20ml and the diethyl ether 60ml of the 0.486g that packs into.After being equipped with agitating vane, thermometer and condenser, it was reacted 16 hours at 21 to 23 ℃.After reaction, the content in the flask is put in the separating funnel of 200ml, separate water layer.With the ion-exchange water washing ether layer of 30ml 3 times.The ether layer is put in the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer,, become constant weight up to it with in 70 to 75 ℃ of dryings of vacuum pump.Obtain the compd E of 1.19g.
1H-NMR(300MHz，DMSO-d
6)
δ7.78(12H，m)，1.32(27H，s)
Embodiment 18 (synthesizing of compound F 17-hydroxy-corticosterone)
With the inside of the four neck flasks of nitrogen replacement 50ml, poly-(1-just-butyl-4-vinylpridine trifluoromethane sulfone imide), compd A 1.088g and the dimethyl formamide 30ml of the 0.309g that packs into.After being equipped with agitating vane, thermometer and condenser, it was reacted 16 hours at 21 to 23 ℃.After reaction, the content in the flask is put in the 200ml separating funnel, add the toluene of 90ml, with the ion exchanged water extraction DMF of 50ml.With the ion-exchange water washing toluene layer of 50ml 3 times.Toluene layer is put in the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate toluene layer by vaporizer,, become constant weight up to it with in 70 to 75 ℃ of dryings of vacuum pump.Obtain the compound F 17-hydroxy-corticosterone of 1.08g.
1H-NMR(300MHz，DMSO-d
6)
δ5.8，7.4，9.1
19F-NMR(300MHz，DMSO-d
6)
δ-132.7，-133.6，-134.8，-157.7，-159.8，-162.5，-164.0，-165.2，-166.0
Synthetic embodiment 19 (compound G's is synthetic)
Synthesizing of sylvite
With the inside of the four neck flasks of nitrogen replacement 200ml, K packs into
2[Ni (CN)
4] 3.01g, three (pentafluorophenyl group) borine 25.5g and diethyl ether 100ml.After being equipped with agitating vane, thermometer and condenser, it was reacted 16 hours at 21 to 23 ℃.The crystal of filter deposition washs this block with the ethyl acetate of 100ml.Clorox with 5% is handled the residue K on strainer
2[Ni (CN)
4].Filtering solution is transferred in the 500ml separating funnel, and with it with the ion-exchange water washing of 100ml 3 times.Organic layer is transferred in the Erlenmeyer flask of 500ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.By vaporizer concentrated solvent at room temperature, obtain the thick block of 31.4g.In thick block, add diethyl ether 50ml and just-hexane 120ml, stirred 2 hours, filtration, with just-hexane 50ml washs this block.By dry being dried under 70 to 75 ℃ of decompressions, become constant weight up to it, obtain the sylvite of 24.4g.
Synthetic embodiment 20 (compound G's is synthetic)
With the inside of the four neck flasks of nitrogen replacement 200ml, the sylvite of packing into 3.0g, diethyl ether 100ml and ion exchanged water 20ml, and be equipped with agitating vane, thermometer and condenser.Under 21 to 23 ℃ of stirrings, dripped 1% hydrochloric acid 15g, stirred then 1 hour in 10 minutes.
Content in the flask is poured in the 200ml separating funnel, separated water layer.With ion-exchange water washing ether layer 3 times.The ether layer is poured in the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer, dry under 70 to 75 ℃ by vacuum pump, become constant weight up to it, obtain the compound G of 2.81g.
19F-NMR(300MHz，DMSO-d
6)
δ-132.7，-133.7，-134.3，-154.8，-157.8，-159.2，-161.0，-162.9，-164.3，-165.4，-165.8，-166.5
Embodiment 21 (synthesizing of compound H)
With the inside of the four neck flasks of nitrogen replacement 200ml, pack 1 into, 1 '-two-2-ethylhexyl-4,4 '-dipyridyl diiodide 0.323g, compd A 1.223g, ion exchanged water 20ml and diethyl ether 60mL.After being equipped with agitating vane, thermometer and condenser, it was reacted 22 hours at 21 to 23 ℃.
Content in the flask is poured into to the 200ml separating funnel, separated water layer.Wash the ether layer 3 times with ion exchanged water 40ml.The ether layer is poured into to the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer.Add toluene 50ml to it, stirred 0.5 hour, after the cooling, filter it at 60 to 65 ℃.Repeated washing process 3 times, dry under 80 to 85 ℃ by vacuum pump, become constant weight up to it.Obtain the compound H of 1.15g.
1H-NMR(270MHz，CD
3OD)
δ9.258(4H，m)，8.687(4H，m)，4.665(4H，d)，2.049(2H，m)，1.387(16H，m)，0.943(12H，m)
Synthetic embodiment 22 (synthesizing of Compound I)
Synthesizing of quaternary salt
With the inside of the four neck flasks of nitrogen replacement 50ml, 1 of the 27.4g that packs into, the n-Octyl Bromide of 8-diazabicyclo [5,4,0] 11 carbon-7-alkene and 11.6g.After being equipped with agitating vane, thermometer and condenser, it was reacted 22 hours at 21 to 23 ℃.After being equipped with agitating vane, thermometer and condenser, it was reacted 5.5 hours at 110 to 115 ℃.After being cooled to 80 ℃, pack into toluene 50ml and hexane 150ml are cooled to 5 ℃ with it.It was stirred 1 hour under being lower than 5 ℃, under this temperature, place, remove supernatant layer liquid by decant.Pack in flask toluene 50ml and hexane 150ml stirred 1 hour at 60 to 65 ℃, and it is cooled to 5 ℃.Under being lower than 5 ℃, stirred 1 hour, under this temperature, place, remove supernatant layer liquid by decant.Repeat this process again, distill residual solvent by vaporizer.Then, by vacuum pump it is dried under 80 to 85 ℃ and becomes constant weight, obtain the 19.5g quaternary salt.
Quaternary salt
1H-NMR (270MHz, CD
3OD)
δ3.676(2H，m)，3.545(6H，m)，2.054(2H，m)，1.722(10H，m)，1.332(10H，m)，0.798(3H，m)
Quaternary salt
Synthetic embodiment 23 (synthesizing of Compound I)
With the inside of the four neck flasks of nitrogen replacement 200ml, the ion exchanged water of the quaternary salt of the 0.590g that packs into, 1.240 compd A, 20ml and diethyl ether 60ml.After being equipped with agitating vane, thermometer and condenser, it was reacted 24 hours at 21 to 23 ℃.After the reaction, the content in the flask is poured into to the separating funnel of 200ml, removed water layer, the ion-exchange water washing ether layer of usefulness 40ml 3 times.
In the Erlenmeyer flask that the ether layer is poured at 200ml, add anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer, and become constant weight up to it with in 80 to 85 ℃ of dryings of vacuum pump.Obtain the Compound I of 1.53g.
Compound I
1H-NMR (270MHz, CD
3OD)
δ3.660(2H，m)，3.520(6，m)，2.064(2H，m)，1.748(10H，m)，1.296(10H，m)，0.867(3H，m)
Embodiment 24 (synthesizing of compound K)
With the inside of the four neck flasks of nitrogen replacement 200ml, 1 of the 0.318g that packs into, the sylvite that 1 '-two-2-ethylhexyl-4,4 '-dipyridyl diiodide, the 1.144g compound G by synthetic embodiment 12 obtains, the diethyl ether of 20ml ion exchanged water and 60ml.After being equipped with agitating vane, thermometer and condenser, it was reacted 18 hours at 21 to 23 ℃.After the reaction, the content in the flask is poured into to the separating funnel of 200ml, added the ethyl acetate of 50ml, remove water layer to it.Then, the ion-exchange water washing organic layer of usefulness 30ml is 3 times.Organic layer is poured into to the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer,, become constant weight up to it with in 80 to 85 ℃ of dryings of vacuum pump.Obtain the compound K of 1.18g.
1H-NMR(270MHz，DMSO-d
6)
δ9.385(4H，d)，8.805(4H，d)，4.634(4H，m)，2.073(2H，m)1.300(16H，m)，0.870(1H，m)
Embodiment 25 (synthesizing of compound L)
With the inside of the four neck flasks of nitrogen replacement 200ml, 1 of the 0.205g that packs into, 1 '-dibenzyl-4,4 '-dipyridyl dichloride, 1.089g compd A, the ion exchanged water of 20mL and the diethyl ether of 60mL.After being equipped with agitating vane, thermometer and condenser, it was reacted 18 hours at 21 to 23 ℃.After the reaction, the content in the flask is poured into to the separating funnel of 200ml, removed water layer.Then, the ion-exchange water washing ether layer of usefulness 30ml is 3 times.The ether layer is added in the Erlenmeyer flask of 200ml, adds anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer,, become constant weight up to it with in 80 to 85 ℃ of dryings of vacuum pump.Obtain the compound L of 1.21g.
1H-NMR(270MHz，DMSO-d
6)
δ9.501(4H，d)，8.733(4H，d)，7.606(4H，m)，7.479(6H，m)
Embodiment 26 (compound M's is synthetic)
With the inside of the four neck flasks of nitrogen replacement 200ml, sylvite, the ion exchanged water of 20ml and the diethyl ether of 60ml that three (4-tert-butyl phenyl sulfonium) trifluoro-methanyl sulfonate of the 0.595g that packs into, 1.144g compound G by synthetic embodiment 12 obtains.After being equipped with agitating vane, thermometer and condenser, it was reacted 16 hours at 21 to 23 ℃.After the reaction, the content in the flask is poured into to the separating funnel of 200ml, added the ethyl acetate of 50ml, remove water layer to it.Then, the ion-exchange water washing organic layer of usefulness 30ml is 3 times.Organic layer is added in the Erlenmeyer flask of 200ml, adds anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate organic layer by vaporizer,, become constant weight up to it with in 80 to 85 ℃ of dryings of vacuum pump.Obtain the compound M of 1.24g.
1H-NMR(300MHz，DMSO-d
6)
δ7.774(12H，m)，1.313(27H，s)
Synthetic embodiment 27 (synthesizing of compound N)
With the inside of the four neck flasks of nitrogen replacement 200ml, the diethyl ether of the compd A of the 1.089g that packs into, the ion exchanged water of 20ml and 50ml.After being equipped with agitating vane, thermometer and condenser, stirring dripped 1% hydrochloric acid down at 10 minutes.After 2 hours, the content in the flask poured in 2 to 00ml the separating funnel, remove water layer.Then, the ion-exchange water washing ether layer of usefulness 30ml is 3 times.The ether layer is poured into to the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate organic layer by vaporizer,, become constant weight up to it with in 80 to 85 ℃ of dryings of vacuum pump.Obtain the compound N of 1.06g.
19F-NMR(300MHz，DMSO-d
6)
δ-132.7，-133.7，-134.3-154.8，-157.8，-159.2，-161.0，-162.9，-164.3，-165.4，-165.8，-166.5
The preparation 1 of＜luminescence polymer liquid composite 〉
In the mixing solutions of toluene/ethyl acetate=80/20 (weight ratio), the mixture of 25: 75 (weight ratio) of dissolving luminescence polymer 1 and luminescence polymer 2, making its amount is 0.9 weight %, right with the amount hybrid ionic shown in the table 1 again, and dissolving.Then, be to filter in Teflon (registered trademark) strainer of 0.2 μ by diameter with it, the preparation coating solution.As for ion pair, use be those of synthetic embodiment.The add-on of ion pair is to show as the weight part with respect to whole luminescence polymers of 100 weight parts.
＜preparation of devices and assessment 〉
Be formed with thereon by sputtering method on the glass baseplate of ITO film that thickness is 150nm, use solution (the Bayer Co. of poly-(Ethylenedioxy Thiophene)/polystyrolsulfon acid, Baytron), forming thickness with rotary coating is the film of 70nm, then with its on hot plate in 200 ℃ of dryings 10 minutes.Then, use coating solution rotary coating under the speed of rotation of 1000rpm of prepared luminescence polymer, form the film of thickness for about 85nm.
In addition, under reduced pressure in 90 ℃ of dryings after 1 hour, as negative electrode, then the aluminium of 100nm is made polymer LED to the LiF by deposition 1nm as the calcium of cathode buffer layer, 5nm with it.Here, all vacuum tightnesss under depositing time are 1 to 9 * 10
-5Holder.
By applying voltage to the device that obtains, the EL that observes luminescence polymer is luminous.The Devices Characteristics that obtains is shown in Table 1.
As for the test in work-ing life, by carrying out the constant-current driving of 10mA, for having 2mm * 2mm (area 4mm
2) the device of luminous component, measure brightness.
With 2000cd/m
2Conversion timing definition in work-ing life for being converted at 2000cd/m
2In work-ing life under the time of the beginning brightness that drives, wherein suppose half work-ing life-time ∝ (beginning brightness)
-1Relation.(Organic EL Material and Display is published 107 pages by CMC (2001)).
Device as for the assessment embodiment 1 to 12 of the luminescence polymer liquid composite preparation that comprises ion pair by use, compare with the device of assessment comparative example 1 by using the luminescence polymer liquid composite preparation do not comprise ion pair, observe the remarkable improvement in work-ing life.
Table 1
| Kind | Add-on (every weight resin %) | Beginning brightness (cd/m under 10mA drives 2) | Half work-ing life under 10mA drives (hour) | 2000cd/m 2Conversion work-ing life (hour) | |
| Assessment embodiment 1 | Compd A | 0.1 | 2200 | 1.9 | 2.1 |
| Assessment embodiment 2 | Compd B | 0.1 | 2960 | 1.8 | 2.7 |
| Assessment embodiment 3 | Compd B | 0.2 | 1821 | 2.4 | 2.2 |
| Assessment embodiment 4 | Compound C | 0.1 | 2240 | 1.4 | 1.6 |
| Assessment embodiment 5 | Compound D | 0.1 | 2620 | 1.1 | 1.4 |
| Assessment embodiment 6 | Compd E | 0.1 | 2750 | 2.3 | 3.2 |
| Assessment embodiment 7 | Compound F 17-hydroxy-corticosterone | 0.1 | 2890 | 1.5 | 2.2 |
| Assessment embodiment 8 | Compound G | 0.1 | 2100 | 1.9 | 2.0 |
| Assessment embodiment 9 | Compound H | 0.2 | 1640 | 4.8 | 3.9 |
| Assessment embodiment 10 | Compound I | 0.2 | 1690 | 1.8 | 1.5 |
| Assessment embodiment 11 | Compound K | 0.1 | 1990 | 3.1 | 3.1 |
| Assessment embodiment 12 | Compound L | 0.1 | 1790 | 2.9 | 2.6 |
| Assessment comparative example 1 | -- | 0.1 | 2760 | 1.85 | 1.2 |
The preparation 1 of＜luminescence polymer liquid composite 〉
In the mixing solutions of toluene/ethyl acetate=80/20 (weight ratio), the mixture of 70: 30 (weight ratio) of dissolving luminescence polymer 3 and luminescence polymer 4, making its amount is 1.2 weight %, right with the amount hybrid ionic shown in the table 2 again, and dissolving.Then, be to filter in Teflon (registered trademark) strainer of 0.2 μ by diameter with it, the preparation coating solution.As for ion pair, use be those of synthetic embodiment.The add-on of ion pair is to show as the weight part with respect to whole luminescence polymers of 100 weight parts.
＜preparation of devices and assessment 〉
Be formed with thereon by sputtering method on the glass baseplate of ITO film that thickness is 150nm, use solution (the Bayer Co. of poly-(Ethylenedioxy Thiophene)/polystyrolsulfon acid, Baytron), forming thickness with rotary coating is the film of 70nm, then with its on hot plate in 200 ℃ of dryings 10 minutes.Then, use coating solution rotary coating under the speed of rotation of 1000rpm of prepared luminescence polymer, form the film of thickness for about 85nm.
In addition, under reduced pressure in 90 ℃ of dryings after 1 hour, as negative electrode, then the aluminium of 100nm is made polymer LED to the LiF by deposition 1nm as the calcium of cathode buffer layer, 5nm with it.Here, all vacuum tightnesss under depositing time are 1 to 9 * 10
-5Holder.
By applying voltage to the device that obtains, the EL that observes luminescence polymer is luminous.The Devices Characteristics that obtains is shown in Table 1.
As for the test in work-ing life, by carrying out the constant-current driving of 10mA, for having 2mm * 2mm (area 4mm
2) the device of luminous component, measure brightness.
With 5000cd/m
2Conversion timing definition in work-ing life for being converted at 5000cd/m
2In work-ing life under the time of the beginning brightness that drives, wherein suppose half work-ing life-time ∝ (beginning brightness)
-1Relation.(Organic EL Material and Display is published 107 pages by CMC (2001)).
Device as for the assessment embodiment 13 to 16 of the luminescence polymer liquid composite preparation that comprises ion pair by use, compare with the device of assessment comparative example 2 by using the luminescence polymer liquid composite preparation do not comprise ion pair, observe the remarkable improvement in work-ing life.
Table 2
| Kind | Add-on (every weight resin %) | Beginning brightness (cd/m under 10mA drives 2) | Half work-ing life under 10mA drives (hour) | 2000cd/m 2Conversion work-ing life (hour) | |
| Assessment embodiment 13 | Compd E | 0.1 | 5830 | 6.5 | 7.6 |
| Assessment embodiment 14 | Compd E | 0.2 | 4730 | 10 | 9.5 |
| Assessment embodiment 15 | Compound M | 0.1 | 6260 | 2.4 | 3.0 |
| Assessment embodiment 16 | Compound N | 0.1 | 4420 | 5.5 | 4.9 |
| Assessment comparative example 2 | 0 | 6070 | 1.5 | 1.8 |
Synthetic embodiment 28
Synthesizing of＜luminescence polymer 5 〉
In dehydration tetrahydrofuran (THF) 1600ml, dissolving 2,7-two bromo-9,9-dioctyl fluorene (26g, 0.047mol), 2,7-two bromo-9,9-diisoamyl fluorenes (5.6g, 0.012mol) and 2, (22g 0.141mol), and replaces the inside of this system to 2 '-dipyridyl with nitrogen bubble.Under nitrogen atmosphere, in this solution, add two (1, the 5-cyclooctadiene) Ni (0) { Ni (COD)
2(40g, 0.15mol), with temperature be elevated to 60 ℃ and the reaction 8 hours.After reaction,, be added drop-wise in the mixing solutions of 25% ammoniacal liquor 200ml/ methyl alcohol 1200mL/ ion exchanged water 1200mL stir about 30 minutes with reaction mixture cool to room temperature (about 25 ℃).The settling of filtering-depositing, and dry air.In toluene 1100mL, after the dissolving,, filtering solution is added drop-wise among the methyl alcohol 3300mL, stirred 30 minutes its filtration.The settling of filtering-depositing, and with methyl alcohol 1000mL washing, drying under reduced pressure is 5 hours then.The output of the luminescence polymer that obtains is 20g.The number-average molecular weight and the weight-average molecular weight of the polystyrene conversion of luminescence polymer 1 are respectively Mn=4.6 * 10
4And Mw=1.1 * 10
5, (mobile phase: chloroform).
The preparation of＜luminescence polymer liquid composite 〉
Dissolving luminescence polymer 5 is 1.5 weight % in toluene, again with the amount mixing salt shown in the table 3, and dissolving.Then, be to filter in Teflon (registered trademark) strainer of 0.2 μ by diameter with it, the preparation coating solution.As for salt, use Rohdorsil light trigger PI-2074 by the Rohdia preparation.The add-on of salt is to show as the weight part with respect to whole luminescence polymers of 100 weight parts.
Table 3
| The add-on of salt | The UV exposure | Under driving, 10mA begins brightness (cd/m 2) | Half work-ing life under 10mA drives (hour) | 100cd/m 2Conversion work-ing life (hour) | |
| Assessment embodiment 17 | 0.05 | Do not carry out | 124 | 47 | 58 |
| Assessment embodiment 18 | 0.05 | Carry out | 223 | 24 | 54 |
| Assessment embodiment 19 | 0.1 | Carry out | 93 | (in the time of 135 hours, being 78%) | ＞＞125 |
| Assessment embodiment 20 | 0.2 | Carry out | 70 | (in the time of 135 hours, being 93%) | ＞＞95 |
| Assessment comparative example 3 | 0 | Do not carry out | 163 | 2.7 | 4.4 |
| Assessment comparative example 4 | 0 | Carry out | 256 | 2.3 | 5.9 |
＜preparation of devices and assessment 〉
Be formed with thereon by sputtering method on the glass baseplate of ITO film that thickness is 150nm, use solution (the Bayer Co. of poly-(Ethylenedioxy Thiophene)/polystyrolsulfon acid, Baytron), forming thickness with rotary coating is the film of 70nm, then with its on hot plate in 200 ℃ of dryings 10 minutes.Then, use coating solution rotary coating under the speed of rotation of 1400rpm of prepared luminescence polymer, form the film of thickness for about 85nm.
Under the situation of carrying out the UV exposure, under nitrogen atmosphere, by the 50W/cm of i line (365nm) measurement
2The high voltage mercury lamp of illumination carries out UV exposure 10 seconds.
In addition, under reduced pressure in 90 ℃ of dryings after 1 hour, as negative electrode, then the aluminium of 100nm is made polymer LED to the LiF by deposition 1nm as the calcium of cathode buffer layer, 5nm with it.Here, all vacuum tightnesss under depositing time are 1 to 9 * 10
-5Holder.
By applying voltage to the device that obtains, the EL that observes luminescence polymer is luminous.The Devices Characteristics that obtains is shown in Table 3.
As for the test in work-ing life, by carrying out the constant-current driving of 10mA, for having 2mm * 2mm (area 4mm
2) the device of luminous component, measure brightness.
With 100cd/m
2Conversion timing definition in work-ing life for being converted at 100cd/m
2In work-ing life under the time of the beginning brightness that drives, wherein suppose half work-ing life-time ∝ (beginning brightness)
-1Relation.(Organic EL Material and Display is published 107 pages by CMC (2001)).
Device as for the assessment embodiment 17 to 20 of the luminescence polymer liquid composite preparation that comprises ion pair by use, compare with 4 device with the assessment comparative example 3 of the luminescence polymer liquid composite preparation that does not comprise ion pair by use, observe the remarkable improvement in work-ing life.
Synthetic embodiment 29
Synthesizing of＜triphenylsulfonium four (pentafluorophenyl group) borate (TPSTB) 〉
In the three-necked flask of 100ml, mix four (pentafluorophenyl group) lithium tetraborates of 0.90g and the chloroform of 10ml.Then, add the aqueous solution that 10ml contains 0.30g triphenyl sulfonium salt, stirred 24 hours.After removing water layer, it is used the ion-exchange water washing.Concentrate chloroformic solution, and dry, recrystallization from methyl alcohol-tert-butyl methyl ether obtains the white solid of 0.80g.
1H-NMR(300MHz/CDCl
3)：δ(ppm)7.50，(d，2H)7.70，(dd，2H)，7.83(dd，1H)
19F-NMR(300MHz/CDCl
3)：d(ppm)-128.85(d，2F)，-159.28(dd，1F)，-163.09(dd，2F)。
Synthetic embodiment 30
Synthesizing of＜trimethylsulfonium four (pentafluorophenyl group) borate (TMeSTB) 〉
In the three-necked flask of 100ml, mix four (pentafluorophenyl group) lithium tetraborates of 0.27g and the chloroform of 10ml.Then, add the aqueous solution that 10ml contains 0.10g triphenyl sulfonium salt, stirred 2 hours.The solid of filter deposition is with chloroform and water washing.Obtain the white solid of 0.18g.
1H-NMR(300MHz/DMSO-d
6)(s，9H)：δ(ppm)2.90
19F-NMR(300MHz/DMSO-d
6)：d(ppm)-132.86(d，2F)，-161.75(dd，1F)，-166.41(dd，2F)。
Synthetic embodiment 31
Synthesizing of＜TBuA four (pentafluorophenyl group) borate (N4B) 〉
With the inside of the two neck flasks of nitrogen replacement 50ml, the tetrabutylammonium chloride of dissolving 0.15g in the water of 4.4mL adds [four (pentafluorophenyl group)] lithium tetraborate-ethyl ether complex compound of 0.44g.In case after the dissolving, deposition solid then.By adding 4.4mL chloroform dissolved solids.After stirring 5 hours, it is carried out layering, and with twice of 5mL chloroform extraction water.After dried over sodium sulfate, distill solvent, obtain 31 of 0.45g.
1H-NMR(300MHz，CDCl
3)
δ3.09-3.03(8H，m)，1.62-1.51(8H，m)，1.42-1.30(8H，m)，0.97(12H，t)
19F-NMR(300MHz，CDCl
3)
δ14.2，10.3，-133.1
MS (ESI-just)
m/z：242
MS (ESI-is negative)
m/z：679
Embodiment 32
1 '-phenylbenzene-4,4 '-dipyridyl two [four (pentafluorophenyl group) borate] synthetic
With the inside of the Schlenk test tube of nitrogen replacement 25ml, in the water of 2.5ml 1 of dissolving 57mg, 1 '-phenylbenzene-4,4 '-dipyridyl dichloride adds [four (pentafluorophenyl group)] lithium tetraborate-ethyl ether complex compound of 250mg.The chloroform that adds 2.5ml stirs them 7 hours.It is carried out layering, filter water and washing.Merge resistates and organic layer, solvent evaporated is so obtain 1 of 129mg, 1 '-phenylbenzene-4,4 '-dipyridyl two [four (pentafluorophenyl group) borate].
1H-NMR(300MHz，DMSO-d
6)
δ 9.71 (4H, d), 9.07 (4H, d), 7.98 (4H, d), 7.83 to 7.79 (6H, m)
19F-NMR(300MHz，DMSO-d
6)
δ-132.8，-161.8，-166.3
Synthetic embodiment 33
(4-{4-(dimethylamino) styryl }-N-picoline four (pentafluorophenyl group) borate) synthetic)
With the inside of the Schlenk test tube of nitrogen replacement 25ml, the 4-of suspension 113mg in the water of 2.5mL (4-(dimethylamino) styryl)-N-picoline iodide adds [four (pentafluorophenyl group)] lithium tetraborate-ethyl ether complex compound of 250mg.The chloroform that adds 2.5ml stirs them 7 hours.It is carried out layering, filter water and washing.Merge resistates and organic layer, solvent evaporated is so obtain 4-{4-(dimethylamino) styryl of 91mg }-N-picoline four (pentafluorophenyl group) borate.
1H-NMR(300MHz，DMSO-d
6)
δ8.69(2H，d)，8.05(2H，d)，7.91(1H，d)，7.60(2H，d)，7.17(1H，d)，6.79(2H，d)，4.18(3H，s)，3.03(6H，s)
19F-NMR(300MHz，DMSO-d
6)
δ-132.8，-161.8，-166.3
Synthetic embodiment 34
(trans-4-{2-(1-ferrocenyl) vinyl }-1-picoline four (pentafluorophenyl group) is boratory synthetic)
With the inside of the Schlenk test tube of nitrogen replacement 25ml, trans-4-[2-(1-ferrocenyl) vinyl suspends in the water of 2.5mL]-1-picoline iodide, add four (pentafluorophenyl group) borate of 250mg.The chloroform that adds 2.5ml stirs them 7 hours.It is carried out layering, filter water and washing.Merge resistates and organic layer, solvent evaporated is so obtain trans-4-{2-(1-ferrocenyl) vinyl of 167mg }-1-picoline four (pentafluorophenyl group) borate.
1H-NMR(300MHz，DMSO-d
6)
δ8.73(2H，d)，8.06(2H，d)，7.89(1H，d)，6.97(2H，d)，4.75(2H，s)，4.60(2H，s)，4.23(5H，s)，4.19(3H，s)
19F-NMR(300MHz，DMSO-d
6)
δ-132.6，-161.8，-166.1
Synthetic embodiment 35
＜four (dodecyl) ammonium four (pentafluorophenyl groups) are boratory synthetic 〉
With the inside of the Schlenk test tube of nitrogen replacement 25ml, four (dodecyl) ammonium chloride of dissolving 225mg in the water of 2.5mL adds four (pentafluorophenyl group) borate of 250mg.The chloroform that adds 2.5ml stirs them 7 hours.It is carried out layering, filter water and washing.Merge resistates and organic layer, solvent evaporated.Obtain four (dodecyl) ammonium four (pentafluorophenyl group) borate of 407mg.
1H-NMR(300MHz，CDCl
3)
δ 3.02 (8H, br), 1.56 (8, br), 1.29 to 1.23 (44H, m), 0.87 (12H, t)
19F-NMR(300MHz，CDCl
3)
δ-132.2，-162.5，-166.5
The preparation of＜luminescence polymer liquid composite 〉
Luminescence polymer 5 is dissolved in the toluene, is 1.5 weight %, and again with metal-salt and the class of the mixing of the amount shown in the table 4 as additive, and dissolving.Then, be to filter in Teflon (registered trademark) strainer of 0.2 μ by diameter with it, the preparation coating solution.As for metal-salt and class, use synthetic embodiment those and following shown in be purchased reagent.Shown metal-salt and add-on be to show as weight part with respect to whole luminescence polymers of 100 weight parts.
LiB: four (pentafluorophenyl groups)] lithium tetraborate-ethyl ether complex compound (product of Toko-Kasei)
AB:N, accelerine four (pentafluorophenyl group)] borate (product of STREM CHEMICALS)
TB: trityl four (pentafluorophenyl group)] borate (product of STREM CHEMICALS)
Table 4
| Kind | Add-on (every weight resin %) | The UV exposure | Beginning brightness (cd/m under 10mA drives 2) | Half work-ing life under 10mA drives (hour) | 100cd/m 2Transform work-ing life (hour) | |
| Assessment embodiment 21 | TPSTB | 0.2 | Do not carry out | 44 | 29 | 12.8 |
| Assessment embodiment 22 | TPSTB | 0.2 | Carry out | 55 | 15 | 8.3 |
| Assessment embodiment 23 | TMeSTB | 0.2 | Do not carry out | 23 | 112 | 25.8 |
| Assessment embodiment 24 | N4B | 0.2 | Do not carry out | 38 | 10 | 3.8 |
| Assessment embodiment 25 | LiB | 0.2 | Do not carry out | 63 | 65 | 41.0 |
| Assessment embodiment 26 | AB | 0.2 | Carry out | 49 | 54 | 26.5 |
| Assessment embodiment 27 | TB | 0.2 | Carry out | 34 | 85 | 28.9 |
| Assessment embodiment 28 | PI2074 | 0.2 | Do not carry out | 54 | 70 | 37.8 |
| Assessment embodiment 29 | PI2074 | 0.2 | Carry out | 48 | 29 | 13.9 |
| Assessment comparative example 5 | - | 0 | Do not carry out | 85 | 1.5 | 1.3 |
| Assessment comparative example 6 | - | 0 | Carry out | 113 | 1.3 | 1.5 |
＜preparation of devices and assessment 〉
Be formed with thereon by sputtering method on the glass baseplate of ITO film that thickness is 150nm, use solution (the Bayer Co. of poly-(Ethylenedioxy Thiophene)/polystyrolsulfon acid, Baytron), forming thickness with rotary coating is the film of 70nm, then with its on hot plate in 200 ℃ of dryings 10 minutes.Then, use coating solution rotary coating under the speed of rotation of 1400rpm of prepared luminescence polymer, form the film of thickness for about 85nm.
Under the situation of carrying out the UV exposure, under nitrogen atmosphere, by the 50W/cm of i line (365nm) measurement
2The high voltage mercury lamp of illumination carries out UV exposure 10 seconds.
In addition, under reduced pressure in 90 ℃ of dryings after 1 hour, as negative electrode, then the aluminium of 100nm is made polymer LED to the LiF by deposition 1nm as the calcium of cathode buffer layer, 5nm with it.Here, all vacuum tightnesss under depositing time are 1 to 9 * 10
-5Holder.
By applying voltage to the device that obtains, the EL that observes luminescence polymer is luminous.The Devices Characteristics that obtains is shown in Table 3.
As for the test in work-ing life, by carrying out the constant-current driving of 10mA, for having 2mm * 2mm (area 4mm
2) the device of luminous component, measure brightness.
With 100cd/m
2Conversion timing definition in work-ing life for being converted at 100cd/m
2In work-ing life under the time of the beginning brightness that drives, wherein suppose half work-ing life-time ∝ (beginning brightness)
-1Relation.(Organic EL Material and Display is published 107 pages by CMC (2001)).
Device as for the assessment embodiment 21 to 29 of the luminescence polymer liquid composite preparation that comprises ion pair by use, compare with 6 device with the assessment comparative example 5 of the luminescence polymer liquid composite preparation that does not comprise ion pair by use, observe the remarkable improvement in work-ing life.
Synthetic embodiment 36
Synthesizing of (three (4-tert-butyl phenyl sulfoniums), four (pentafluorophenyl groups)) borate (TTBPSTB))
With the inside of the four neck flasks of nitrogen replacement 200ml, three (4-tert-butyl phenyl sulfonium) trifluoro-methanyl sulfonate of the 0.581g that packs into, 0.834g four (pentafluorophenyl group)) lithium tetraborate-ethyl ether complex compound, the ion exchanged water of 20ml and the diethyl ether of 60ml.After being equipped with agitating vane, thermometer and condenser, it was reacted 16 hours at 21 to 23 ℃.After reaction, the content in the flask is put in the 200ml separating funnel, remove water layer.Then, the ion-exchange water washing ether layer of usefulness 30ml is 3 times.The ether layer is put in the Erlenmeyer flask of 200ml, added anhydrous sodium sulphate, filter out anhydrous sodium sulphate with dehydration.At room temperature concentrate the ether layer by vaporizer,, become constant weight up to it with in 70 to 75 ℃ of dryings of vacuum pump.Obtain the compound (TTBPSTB) of 1.04g.
1H-NMR(270MHz，DMSO-D
6)
δ7.78(12H，m)，1.31(27H，s)
The preparation of＜luminescence polymer liquid composite 〉
In the mixing solutions of toluene/ethyl acetate=80/20 (weight ratio), the mixture of 70: 30 (weight ratio) of dissolving luminescence polymer 3 and luminescence polymer 4, making its amount is 1.2 weight %, right with the amount hybrid ionic shown in the table 5 again, and dissolving.Then, be to filter in Teflon (registered trademark) strainer of 0.2 μ by diameter with it, the preparation coating solution.As for ion pair, use be those of synthetic embodiment.The add-on of ion pair is to show as the weight part with respect to whole luminescence polymers of 100 weight parts.
＜preparation of devices and assessment 〉
Be formed with thereon by sputtering method on the glass baseplate of ITO film that thickness is 150nm, use solution (the Bayer Co. of poly-(Ethylenedioxy Thiophene)/polystyrolsulfon acid, Baytron), forming thickness with rotary coating is the film of 70nm, then with its on hot plate in 200 ℃ of dryings 10 minutes.Then, use coating solution rotary coating under the speed of rotation of 1000rpm of prepared luminescence polymer, form the film of thickness for about 85nm.
In addition, under reduced pressure in 90 ℃ of dryings after 1 hour, as negative electrode, then the aluminium of 100nm is made polymer LED to the LiF by deposition 1nm as the calcium of cathode buffer layer, 5nm with it.Here, all vacuum tightnesss under depositing time are 1 to 9 * 10
-5Holder.
By applying voltage to the device that obtains, the EL that observes luminescence polymer is luminous.The Devices Characteristics that obtains is shown in Table 3.
As for the test in work-ing life, by carrying out the constant-current driving of 10mA, for having 2mm * 2mm (area 4mm
2) the device of luminous component, measure brightness.
With 5000cd/m
2Conversion timing definition in work-ing life for being converted at 5000cd/m
2In work-ing life under the time of the beginning brightness that drives, wherein suppose half work-ing life-time ∝ (beginning brightness)
-1Relation.(Organic EL Material and Display is published 107 pages by CMC (2001)).
Device as for the assessment embodiment 30 of the luminescence polymer liquid composite preparation that comprises ion pair by use, compare with the device of assessment comparative example 7 by using the luminescence polymer liquid composite preparation do not comprise ion pair, observe the remarkable improvement in work-ing life.
Table 5
| Kind | Add-on (every weight resin %) | Beginning brightness (cd/m under 10mA drives 2) | Half work-ing life under 10mA drives (hour) | 100cd/m 2Transform work-ing life (hour) | |
| Assessment embodiment 30 | TTBPSTB | 0.2 | 3210 | 9 | 5.8 |
| Assessment comparative example 7 | - | 0 | 6070 | 1.5 | 1.8 |
Comprise the luminescent layer of luminescent-polymer composition of the present invention by use, can prolong the work-ing life of luminescent device.Therefore, preferably will use the polymer LED of luminescent-polymer composition of the present invention to be used for device, for example the bending used of liquid-crystal display or zero diopter source are as backlight, sectional type indicating meter, dot matrix flat-panel monitor etc.
Claims (18)
1. luminescent-polymer composition, it comprises luminescence polymer and ion pair, and the negatively charged ion of ion pair is by following formula (1a), (1b), (2) or (3) expression,
(wherein, Y
1Represent the 13rd family's atom; Ar
1Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
1Expression Sauerstoffatom or direct key; X
1Expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio, cyano group or the nitro of replacement; A represents 1 to 3 integer, and k represents 1 to 4 integer, V
1Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N=N-, or direct key; B represents 2 to 6 integer; And Z
1Expression-M ' (=O) p-(wherein, the atom of M ' expression the 3rd family, the 4th family, the 5th family, the 6th family, the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family, the 14th family, the 15th family, the 16th family or the 17th family; Represent 0 to 2 integer with p), or Z
1Expression b valency aliphatic alkyl, b valency aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-,-N=N=N-,-NH-,-NH
2-,-OH-or direct key; But, work as Z
1For-C ≡ N-,-N=N=N-,-NH-,-NH
2-or-during OH-, b=2; Z
1And V
1Different mutually, work as Q
1And Ar
1Exist when a plurality of, they each other can be identical or different; A plurality of V
1Can be identical or different; C represents 1 to 6 integer),
(wherein, Y
2Represent the 13rd family's atom; Ar
2Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
2Expression Sauerstoffatom or direct key; X
2Expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-of replacement, the silylthio-of replacement, the silylamino-of replacement, amino, amide group, acid imide base, acyloxy, unit price heterocyclic radical, heteroaryloxy, heteroarylthio, cyano group or the nitro of replacement; D and d ' represent 1 or 2 independently of one another; V
2Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-or-N=N-; A plurality of Y
2, Ar
2, Q
2And V
2Can be identical or different; Work as X
2Exist when a plurality of, they can be identical or different; Represent 1 to 6 integer with e),
(wherein, Y
3Represent the 13rd family's atom; Ar
3Expression contains the aryl of electron withdrawing group, or contains the unit price heterocyclic radical of electron withdrawing group; Q
3Expression Sauerstoffatom or direct key; V
3Represent the 16th family's atom, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, bidentate heterocyclic radical ,-C ≡ N-or-N=N-; A plurality of Y
3, Ar
3, Q
3And V
3Can be identical or different; Represent 1 to 6 integer with f).
2. according to the luminescent-polymer composition of claim 1, wherein, at following formula (1a) with the Ar (1b)
1, the Ar in following formula (2)
3With the Ar in following formula (3)
3It is the perfluor aryl.
3. according to the luminescent-polymer composition of claim 1 or 2, wherein in following formula (1a), a is 2 or 3.
4. according to the luminescent-polymer composition of claim 1 or 2, wherein in following formula (1b), k be for 3 or more than.
5. according to the luminescent-polymer composition of claim 1, wherein following formula (1b) is following formula (6),
[B(Ar
4)
4]
- (6)
(wherein, Ar
4Expression is by two or more phenyl that are selected from those replacements in fluorine and the trifluoromethyl; Ar
4Can be identical or different mutually).
6. according to any one luminescent-polymer composition of claim 1 to 3, wherein, in following formula (1a), Z
1Or V
1For-C ≡ N-.
7. according to claim 1,2,3 and 6 any one luminescent-polymer compositions, wherein, the negatively charged ion of following formula (1a) is by following formula (5-1) or (5-2) expression,
[(C
6F
5)
3B-C≡N-B(C
6F
5)
3]
- (5-1)
[M{C≡N-B(C
6F
5)
3}
4]
2- (5-2)
(wherein, M represents nickle atom or palladium atom).
8. according to any one luminescent-polymer composition of claim 1 to 7, wherein, the positively charged ion of ion pair is hydrogen ion, metallic cation or carbonium ion; Or be selected from element in nitrogen-atoms, Sauerstoffatom, phosphorus atom, sulphur atom, chlorine atom, selenium atom, bromine atoms, tellurium atom and the iodine atom.
9. luminescent-polymer composition according to Claim 8, wherein nitrogen-atoms is divalence by following formula (10) expression,
(wherein, R
3And R
4Represent alkyl, alkoxyl group, aryl, aryloxy, arylalkyl, alkoxy aryl, acyl group, acyloxy, unit price heterocyclic radical or heteroaryloxy independently of one another; R
5And R
6Represent halogen atom independently of one another, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, the siloxy-that replaces, the silylthio-that replaces, the silylamino-that replaces, the amino that replaces, amide group, the acid imide base, acyloxy, the unit price heterocyclic radical, heteroaryloxy, heteroarylthio, acyl group, the imines residue, the silyl that replaces, alkoxy carbonyl, aryloxycarbonyl, aryl-alkoxy carbonyl, the heteroaryloxy carbonyl, carboxyl, cyano group or nitro; T represents direct key, divalence aliphatic alkyl, divalence aromatic hydrocarbyl, alkenylene, ethynylene or divalent heterocycle; I and j independently represent 0 to 4 integer separately; When there being two or more R respectively
5And R
6The time, they can be identical or different).
10. according to any one luminescent-polymer composition of claim 1 to 8, wherein, luminescence polymer comprises the repeating unit by following formula (4) expression,
(wherein, A represents to be used for forming with 4 carbon atoms on two phenyl ring of this formula the atom or the atomic group of 5 yuan of rings or 6 yuan of rings; R
4a, R
4b, R
4c, R
5a, R
5bAnd R
5cRepresent hydrogen atom independently of one another, halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, arylalkyl, alkoxy aryl, alkylthio-aryl, alkenyl, alkynyl, aryl alkenyl, aromatic yl polysulfide yl, acyl group, acyloxy, amide group, the acid imide base, the imines residue, the amino that replaces, the silyl that replaces, the siloxy-that replaces, the silylthio-that replaces, the silylamino-that replaces, cyano group, nitro, the unit price heterocyclic radical, heteroaryloxy, heteroarylthio, alkoxy carbonyl, aryloxycarbonyl, aryl-alkoxy carbonyl, heteroaryloxy carbonyl or carboxyl; R
4bAnd R
4cTogether, and R
5bAnd R
5cCan form ring respectively together).
11. according to any one luminescent-polymer composition of claim 1 to 10, wherein, based on the luminescence polymer of 100 weight parts, the content of ion pair is 0.001 to 10 weight part.
12. a luminescence polymer liquid composite wherein also comprises solvent according to any one luminescent-polymer composition of claim 1 to 11.
13. a polymer light-emitting device, it is included in the luminescent layer between the electrode of being made up of anode and negative electrode, and wherein luminescent layer comprises according to any one luminescent-polymer composition of claim 1 to 11.
14. a polymer light-emitting device, it is included in the luminescent layer between the electrode of being made up of anode and negative electrode, and wherein luminescent layer is by being formed by the luminescence polymer liquid composite that uses claim 12.
15. according to the polymer light-emitting device of claim 13 or 14, wherein said device is by after forming luminescent layer, heat-treats under 50 ℃ or above temperature and makes.
16. an ion pair, wherein negatively charged ion is to be pyridylium, phosphonium cation or iodine positively charged ion by following formula (5-1) expression and positively charged ion,
[(C
6F
5)
3B-C≡N-B(C
6F
5)
3]
- (5-1)
17. an ion pair, wherein negatively charged ion is to be pyridylium, quaternary ammonium cation, phosphonium cation, oxygen positively charged ion, sulfonium cation or iodine positively charged ion by following formula (5-2) expression and positively charged ion,
[M{C≡N-B(C
6F
5)
3}
4]
2- (5-2)
(wherein, M represents nickle atom or palladium atom).
18. the ion pair by following formula (12) expression,
(wherein, R
3, R
4, R
5, R
6Represent and top identical implication with T).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102165032A (en) * | 2008-08-25 | 2011-08-24 | 金泰克斯公司 | Electrochromic compounds and associated media and devices |
| CN102576812A (en) * | 2009-10-01 | 2012-07-11 | 日立化成工业株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| US9156868B2 (en) | 2007-04-19 | 2015-10-13 | Novaled Ag | Aryl-substituted and/or heteroaryl-substituted main group element halides and/or pseudohalides, use of main group element halides and/or pseudohalides, organic semiconducting matrix material, electronic and optoelectronic components |
| CN110268541A (en) * | 2017-02-07 | 2019-09-20 | 日产化学株式会社 | Charge-transporting varnish |
| CN115073780A (en) * | 2022-06-25 | 2022-09-20 | 天津农学院 | Force induced fluorescence enhancement polymer and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011292471A1 (en) * | 2010-08-20 | 2013-03-07 | Centre National De La Recherche Scientifique | Polymer compositions, polymer films, polymer gels, polymer foams, and electronic devices containing such films, gels, and foams |
-
2004
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9156868B2 (en) | 2007-04-19 | 2015-10-13 | Novaled Ag | Aryl-substituted and/or heteroaryl-substituted main group element halides and/or pseudohalides, use of main group element halides and/or pseudohalides, organic semiconducting matrix material, electronic and optoelectronic components |
| TWI583693B (en) * | 2007-04-19 | 2017-05-21 | 諾瓦發光二極體股份公司 | Aryl-and/or heteroaryl-substituted main group element halides and/or pseudohalides, use of main group element halides and/or pseudohalides, organic semiconducting matrix material, electronic and optoelectronic structural elements |
| CN102165032A (en) * | 2008-08-25 | 2011-08-24 | 金泰克斯公司 | Electrochromic compounds and associated media and devices |
| CN102576812A (en) * | 2009-10-01 | 2012-07-11 | 日立化成工业株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| US9583714B2 (en) | 2009-10-01 | 2017-02-28 | Hitachi Chemical Company, Ltd. | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| CN110268541A (en) * | 2017-02-07 | 2019-09-20 | 日产化学株式会社 | Charge-transporting varnish |
| CN115073780A (en) * | 2022-06-25 | 2022-09-20 | 天津农学院 | Force induced fluorescence enhancement polymer and preparation method thereof |
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| Publication number | Publication date |
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| CN100516165C (en) | 2009-07-22 |
| CN101624397A (en) | 2010-01-13 |
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