WO2007003520A1

WO2007003520A1 - Fluorescent diketopyrrolopyrroles and derivatives

Info

Publication number: WO2007003520A1
Application number: PCT/EP2006/063527
Authority: WO
Inventors: Hidetaka Oka; Hiroshi Yamamoto; Junichi Tanabe
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 2005-07-05
Filing date: 2006-06-26
Publication date: 2007-01-11

Abstract

The present invention relates to fluorescent compounds of the formula (I), or (II), (III), a process for their preparation and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, dye lasers and electroluminescent devices. A luminescent device comprising a compound according to the present invention is high in the efficiency of electrical energy utilisation and high in luminance.

Description

Fluorescent Diketopyrrolopyrroles and Derivatives

The present invention relates to fluorescent diketopyrrolopyrroles (DPPs) and derivatives of the formula

a process for their preparation and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, dye lasers and electroluminescent devices. A luminescent device comprising a compound according to the present invention is high in the efficiency of electrical energy utilisation and high in luminance, preferably with a blue to greenish blue emission.

US-B-4,778,899 relates to a process for the preparation of DPPs of the formula I, wherein X and Y are -NH, and A¹ and A² are independently of each other an alkyl or aralkyl group or an isocyclic or heterocyclic aromatic radical. The following alkyl-substituted pyrrolopyrroles are explicitly mentioned:

US-A-5,969,154 describes liquid crystalline compounds. The following alkyl-substituted pyrrolopyrroles are explicitly mentioned:

T. Mukai et al., Chem. Letters (1985) 1809-1812 relates to the Synthesis and properties of 1 ,4-dihydropyrrolo[3,2-b]pyrrole-2,5-dione derivatives. The following pyrroles are explicitly mentioned:

EP-A-648770, WO90/01480, JP-A2 2,296,891 (Ricoh), JP-A2 5,320,633 (Sumitomo), JP-A2 9003448 (Toyo), EP-A-499,011 , WO98/33862, EP-A-1087005, EP-A-1087006, WO03/002672, PCT/EP03/00650, EP-A-1 ,253,151 and WO03/048268 disclose diketopyrrolopyrroles having a fluorescent peak wavelength in the range of 500 to 720 nm.

JP-A2 9003448 (Toyo) describes an organic EL element having between a pair of electrodes a luminous layer containing a DPP-compound as electron-transporting material or an organic compound thin film layer including a luminous layer and an electron-injecting layer wherein the electron-injecting layer contains a DPP compound as the electron-transporting material. The following three heteroarylpyrrolopyrroles are explicitly mentioned:

, and Surprisingly, it was found that luminescent devices, which are high durability besides high in the efficiency of electrical energy utilisation and high in luminance, can be obtained if specific DPP compounds or specific combinations of DPP compounds are used, especially as light emitting substances.

Accordingly, the present invention relates to fluorescent compounds of the formula

wherein

X = O, -N-R¹ and Y = O, -N-R², wherein R¹ and R² may be the same or different and are selected from a C₁-C₂₅alkyl group, which can optionally be interrupted by one or more oxygen atoms and/or can optionally be substituted by a hydroxyl group, an alkoxy group or an amino group; an allyl group, which can be substituted one to three times with C₁-C₃alkyl, a cycloalkyl group, which can optionally be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, a cycloalkyl group, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; an alkenyl group, a cycloalkenyl group, an alkynyl group, a heterocyclic group, haloalkyl, haloalkenyl, haloalkynyl, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, aryl, heteroaryl, or - CR³R⁴-(CH₂)_m-A³ wherein R³ and R⁴ independently from each other stand for hydrogen or C₁-C₄alkyl, or phenyl which can be substituted one to three times with C₁-C₃alkyl, A³ stands for aryl, or heteroaryl, in particular phenyl or 1- or 2-naphthyl which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and m stands for 0, 1 , 2, 3 or 4, A¹, A³ and A⁵ stand independently of each other for hydrogen, cycloalkyl, especially cyclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or phenyl groups, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times

with C₁-C₄-alkyl, halogen, nitro, or cyano; 2-adamantyl, or 1-adamantyl; alkynyl;

or

, wherein m is as defined above,

R⁵, R⁶, R⁷, R⁵, R⁶ and R⁷ may be the same or different and are selected from hydrogen, C₁- C₂₅alkyl, which optionally can be substituted by a hydroxyl group, an alkoxy group, an amino group, a heterocyclic group, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, aryl, or heteroaryl; cycloalkyl, especially cvclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or C₆-Ci₄aryl groups, especially phenyl, or naphthyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; 2-adamantyl, or 1-adamantyl; aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, heteroaryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carboxyl group, an ester group, a carbamoyl group, an amino group, which can optionally be substituted by an alkyl group, alkyl aryl group, an aryl group, a heteroaryl group, an heterocyclic group, or an aralkyl group, or two substituents on the nitrogen atom together with the nitrogen atom to which they are bonded form a five or six membered heterocyclic ring; a nitro group, a silyl group, or a siloxanyl group;

A², A⁴ and A⁶ stand independently of each other for A¹, an unsubstituted, or substituted aryl group, or a unsubstituted, or substituted heteroaryl group.

A⁷ isalkylene, alkenylene, alkynylene, allylene, arylene, or heteroarylene, which is optionally substituted one to three times with C₁-C₈-alkyl, or C₁-C₈-alkoxy, with the proviso that the following compounds of formula I are excluded, wherein X and Y are N-R¹ and N-R², respectively:

and with the additional proviso that the following compounds of formula III are excluded, wherein X and Y are N-R¹ and N-R², respectively :

EL devices employing a DPP of formula I, Il and/or III as light emitting materials can show advanced performance (EL intensity; chromaticity for blue emission at shorter wavelength (< 500 nm)).

If X is -N-R¹ and Y is -N-R², at least one of R¹ and R², preferably both of R¹ and R² are different from a hydrogen atom.

R¹ and R² independently from each other stand, preferably, for C₁-C₈alkyl, C₅-Ci₂-cycloalkyl, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, or -CR³R⁴-(CH₂)_m-A³ , wherein R³ and R⁴ stand for hydrogen, or C₁-C₄alkyl, A³ stands for phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and m stands for 0 or 1 , especially C₁-C₈alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2- dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, tri(C₁- C₈alkyl)silyl, such as trimethylsilyl, -CH₂-A³', -CHCH₃-A³ Or -CH₂-CH₂-A³, wherein A³ stands for phenyl, which can be substituted one or two times with C₁-C₈alkyl.

Most preferred R¹ and R² are the same and stand for C₁-C₈alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2- dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl.

A¹, A³ and A⁵ stand, preferably, independently of each other for cycloalkyl, especially cyclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or phenyl groups, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; 2-adamantyl, or 1-adamantyl;

or

, wherein R^5', R⁶ and R⁷ may be the same or different and are selected from hydrogen, C₁-C₂₅alkyl, cycloalkyl, especially cyclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or C₆-Ci₄aryl groups, especially phenyl, or naphthyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times with C₁- C₄-alkyl, halogen, nitro, or cyano; 2-adamantyl, or 1-adamantyl; a heterocyclic group, halogen, haloalkyl, or an amino group, which can optionally be substituted by an alkyl group, alkylarγl group, an aryl group, a heteroaryl group, an heterocyclic group, or an aralkyl group, or two substituents on the nitrogen atom together with the nitrogen atom to which they are bonded form a five or six membered heterocyclic ring.

In a preferred embodiment of the present invention A¹, A³ and A⁵ stand for a group

, wherein m is 0, or 1 , R⁵ and R⁷ are independently of each other C₁-

C₄alkyl, or hydrogen and R⁶ stands for a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Examples of such aryl and heteroaryl groups are given below in the description of A², A⁴ and A⁶. In said embodiment R⁵ and R⁷ are preferably different from hydrogen.

In another preferred embodiment the present invention relates to compounds of formula

, wherein R¹ and R² are independently of each other an aryl group, or a group -CR³R⁴-(CH₂)_m-A³ , wherein A³ is an aryl group, especially a polycyclic aryl group and m is 0, or 1. Examples of such aryl groups are given below in the description of A², A⁴ and A^6'.

Most preferred A¹, A³ and A⁵ stand for C₁-C₂₅alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n- hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl; cycloalkyl, especially cyclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or phenyl groups, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times

with C₁-C₄-alkyl, such as , , , and wherein A²⁰ and A²¹ are independently of each other a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or 1-adamantyl. Examples of such aryl and heteroaryl groups are given below in the description of A², A⁴ and A^6'. Examples of

such aryl substituted cyclohexans are

In a preferred embodiment of the present invention A², A⁴ and A⁶ stand independently of each other for A¹.

In another preferred embodiment of the present invention A², A⁴ and A⁶ stand independently of each other for an unsubstituted, or substituted aryl group, or a unsubstituted, or substituted heteroarγl group.

In said embodiment A², A⁴ and A⁶ stand, preferably, independently of each other for

, wherein

X is N, or C-R⁸,

R⁵ to R¹¹ may be the same or different and are selected from hydrogen, C₁-C₂₅alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, heteroarγl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR²⁷R²⁸, wherein R²⁷ and R²⁸ independently of each other stand for a hydrogen atom, an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted heterocyclic group, an aralkyl group, or R²⁷ and R²⁸ together with the nitrogen atom to which they are bonded form a five or six membered heterocyclic ring, which can be condensed by one or two optionally substituted phenyl groups, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, or at least two adjacent substituents R⁵ to R¹¹ form an aromatic, heteroaromatic, or aliphatic fused ring system, or

A², A⁴ and A⁶ stand independently of each other for

wherein R¹⁰¹ to R¹²³ may be the same or different and are selected from hydrogen, C₁- C₂₅alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR²⁷R²⁸, wherein R²⁷ and R²⁸ are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, or at least two adjacent substituents R¹¹⁵ to R¹²¹ form an aromatic, heteroaromatic or aliphatic fused ring system, R¹²⁴ and R¹²⁵ may be the same or different and are selected from C₁-C₁₈alkyl; C₁-C₁₈alkoxy, A³, C₆-C₁₈aryl; C₇-Ci ₈aralkyl; or R¹²⁴ and R¹²⁵ together form a ring especially a five-, six- or seven-membered ring, which can optionally be substituted by C₁-C₈alkyl, or which can optionally be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano; or A², A⁴ and A⁶ stand independently of each other for

, wherein

R and R are independently of each other a hydrogen atom, a C₁-C₁₈alkyl group, a C₁-

C₁₈alkoxy group, a group of formula

, or wherein R³¹⁸, R³¹⁹ and R³²⁰ independently from each other stand for hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl, and R³¹⁷ stands for is a hydrogen atom, a C₁-C₂₅alkyl group, which might be interrupted by -O-, a cycloalkyl group, a C₇-C₁₈aralkyl group, a C₆-C₁₈aryl group, or a heterocyclic group, which may be substituted by G; wherein

G is C₁-C₁₈alkyl, -OR³²⁵, -SR³²⁵, -NR³²⁵R³²⁶, -COR³²⁸, -COOR³²⁷, -OCOOR³²⁷, -CONR³²⁵R³²⁶,

-CN, or halogen; wherein R³²⁵ and R³²⁶ are independently of each other C₆-C₁₈aryl; C₆- C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by -0-; or R³²⁵ and R³²⁶ together form a five or six membered ring, in particular

R³²⁷ is C₇-Ci₂alkylaryl; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by -O-;

R³²⁸ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl;

C₇-Ci₂alkylaryl, or C₁-C₁₈alkyl which is interrupted by -O-; or

wherein R¹³¹ to R¹⁵² may be the same or different and are selected from hydrogen, C₁- C₂₅alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR²⁷R²⁸, wherein R²⁷ and R²⁸ are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group,

R¹⁵³ is a hydrogen atom, a C₁-C₂₅alkyl group, which might be interrupted by -O-, a cycloalkyl group, an aralkyl group, an aryl group, or a heterocyclic group. The term "aryl group" is typically C₆-C₃oaryl, such as phenyl, biphenyl, pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl, as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, anthracenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, picenyl, perylenyl, pentacenyl, pentaphenyl, hexacenyl, or hexaphenyl, which can optionally be substituted by one, two, or three, preferably C₁-C₈alkyl groups, or C₁-C₈alkoxy groups.

In said embodiment polycyclic aryl group are preferred, such as pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl, as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, anthracenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, picenyl, perylenyl, pentacenyl, pentaphenyl, hexacenyl, or hexaphenyl, which can optionally be substituted by one, two, or three C₁-C₈alkyl groups, or C₁-C₈alkoxy groups.

If A , A and A are an aryl group, they stand preferably for

wherein R and R are independently of each other

,or

wherein R , R^JU and R are independently of each other hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy

or a group -NR³²R³³, wherein R³² and R³³ are independently of each other

, or

, wherein R³⁴ is hydrogen, C₁-C₈alkyl or C₁-C₈alkoxy, or R²⁷ and R²⁸ together with the nitrogen atom to which they are bonded form a five or six membered

heterocyclic ring, such as

R²¹⁶

which can be condensed by one or two optionally substituted phenyl groups, such as

, wherein R²¹⁶ and R²¹⁷ independently from each other stands for hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl, and

X¹ stands for hydrogen, or C₁-C₈-alkyl;

R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁶, R¹⁰⁷, R¹¹⁰, R¹¹¹, R¹¹², R¹¹⁵, R¹¹⁶, R¹²², R¹²³, R¹³⁵, R¹³⁶, or R¹³⁷ are independently of each other hydrogen, C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-

C₈alkoxy, C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group;

R¹²⁴ and R¹²⁵ may be the same or different and are selected from C₁-C₁₈alkyl; or R¹²⁴ and

R¹²⁵ together form a ring, especially a five-, six- or seven-membered ring, which can optionally be substituted by C₁-C₈alkyl, or which can optionally be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano; and

R²⁵¹, R²⁵², R²⁵³, R²⁵⁴, R²⁵⁵ and R²⁵⁶ are independently of each other C₁-C₈-alkyl, C₁-C₈-alkoxy,

halogen and cyano, in particular hydrogen, especially

, or . wherein R³⁰⁰ is C₁-

C₈alkyl, phenyl, which can be substituted by one, or more C₁-C₈alkyl, or C₁-C₈alkoxy groups, R¹¹⁵ is hydrogen, phenyl, or 1-naphthyl, which can be substituted by one, or more C₁-C₈alkyl, or C₁-C₈alkoxy groups; C₁-C₈alkyl, or C₁-C₈alkoxy, R¹²⁴ and R¹²⁵ are C₁-C₈alkyl or C₁-C₈alkoxy, and R³⁰ is hydrogen, C₁-C₈alkyl or C₁-C₈alkoxy.

If R¹²⁴ and R¹²⁵ together form a ring, they form preferably a cyclopentane, or cyclohexane ring, which can optionally be substituted by one to three times with C₁-C₈alkyl, or which can optionally be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano. Examples of condensed cyclopentyl

and cyclohexyl groups are:

or

, wherein R²⁵¹, R²⁵², R²⁵³, R²⁵⁴, R²⁵⁵ and R²⁵⁶ are independently of each other C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particular hydrogen. The term "heteroaryl or heterocyclic group" is a ring with five to seven ring atoms, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 21-l-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can optionally be substituted by one, two, or three, preferably C₁-C₈alkyl groups, or C₁-C₈alkoxy groups.

If A², A⁴ and A⁶ are derived from a heteroaryl group, they are preferably a group of formula

A' is preferably a single bond, -CO-, -COO-, -S-, -SO-, -SO₂-, -0-, -(CA¹⁴A¹⁵)_n8-

n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1 to 3, n8 is an integer of 1 to 10,

A⁶ and A⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by

E' and/or interrupted by D', C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G', C₂-

C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G', C₂-Ci ₈alkenyl, C₂-Ci ₈alkynyl, C₁- C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E' and/or interrupted by D', C₇-C₂₅aralkyl, or -

CO-A²⁸,

A⁸ is C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E' and/or interrupted by D', C₆-C₂₄ aryl, or C₇-C₂₅aralkyl,

A⁹ and A¹⁰ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E' and/or interrupted by D', C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G', C₂-C₂₀heteroaryl,

C₂-C₂₀heteroaryl which is substituted by G', C₂-Ci ₈alkenyl, C₂-Ci ₈alkynyl, C₁-C₁₈alkoxy, C₁- C₁₈alkoxy which is substituted by E' and/or interrupted by D', or C₇-C₂₅aralkyl, or

A⁹ and A¹⁰ form a ring, especially a five- or six-membered ring, which can optionally be substituted by one or more C₁-C₁₈ alkyl groups; A¹⁴ and A¹⁵ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E' and/or interrupted by D', C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G', C₂-

C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G', D' is -CO-; -COO-; -S-; -SO-; -SO₂-; -O-; -NA²⁵-; -SiA³⁰A³¹-; -POA³²-; -CA²³=CA²⁴-; or -C≡C-; and

E' is -OA²⁹; -SA²⁹; -NA²⁵A²⁶; -COA²⁸; -COOA²⁷; -CONA²⁵A²⁶; -CN; -OCOOA²⁷; or halogen; G' is E', or C₁-C₁₈alkyl; wherein A²³, A²⁴, A²⁵ and A²⁶ are independently of each other H; C₆- C₁₈aryl; C₆-Ci ₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁- C₁₈alkyl which is interrupted by -0-; or A²⁵ and A²⁶ together form a five or six membered ring,

in particular

A²⁷ and A²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by -0-, A²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁- C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by -O-,

A³⁰ and A³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and A³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl.

Examples of especially preferred groups A are:

e independently of each other C₁-C₁₈alkyl, or cyclohexan,

wherein A⁶ and A⁷ are independently of each other H, or C₁-C₁₈alkyl, or

Among the above-mentioned compounds of formula I, Il and III the following compounds are preferred:

(1Mb), wherein the compounds of formula Ia, Ma and MIa are most preferred.

Compounds of formula (I), (M), or (III), wherein X and Y are -NH, and A¹, A², A³, A⁴, A^7', A^5' and A⁶ are as defined above, are intermediates in the preparation of compounds of formula (I), (II), or (III), wherein X and Y are different from -NH. Accordingly the present invention relates also to compounds of formula (I), (II), or (III), wherein X and Y are -NH, and A¹, A², A³, A⁴, A⁷ , A⁵ and A⁶ are as defined above with the proviso that the following compounds of formula I are excluded:

is excluded, wherein X and Y are NH:

The following compounds are most preferred:

The wording "at least two adjacent substituents form an aromatic or aliphatic fused ring system" means two adjacent substituents can form an aromatic ring, such as a phenyl or naphthyl ring, an aliphatic ring, such as a cyclohexyl ring, or a heterocyclic ring, such as a pyridine or pyrrole ring, wherein two or more of such rings can form a fused ring system with the group to which they are bonded.

Compounds of formula I can be prepared, for example, via the following reaction sequence:

wherein R¹, A¹ and A² are as defined above and X¹⁰ is halogen such as chlorine, bromine or iodine, preferably bromine or iodine.

Compounds of formula Il can be prepared, for example, via the following reaction sequence:

wherein R¹, X¹⁰, A⁴ and A⁷ are as defined above and R is C₁-C₁₈alkyl, in particular C₁-C₄alkyl, aryl, in particular phenyl, or aralkyl, in particular benzyl, which can be substituted one to three times with C₁-C₈alkyl, C₁-C₈alkoxy, or halogen. Compounds of formula

be prepared according or in analogy to the method described in US-B-4,778,899.

The compound of formula III is synthesized according, or in analogy described to the method disclosed in Synlett 15 (2003) 2389-2391.

The term "halogen" means fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl is typically linear or branched - where possible - methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethyl butyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl, preferably C₁-C₈alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl- propyl, n-hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethyl butyl and 2-ethylhexyl, more preferably C₁-C₄alkyl such as typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl.

The terms "haloalkyl, haloalkenyl and haloalkynyl" mean groups given by partially or wholly substituting the above-mentioned alkyl group, alkenyl group and alkynyl group with halogen, such as trifluoromethyl etc. The "aldehyde group, ketone group, ester group, carbamoyl group and amino group" include those substituted by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted. The term "silyl group" means a group of formula -SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are independently of each other a C₁-C₈alkyl group, in particular a C₁-C₄alkyl group, a C₆-C₂₄aryl group or a C₇-Ci₂aralkylgroup, such as a trimethylsilyl group. The term "siloxanyl group" means a group of formula -0-SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are as defined above, such as a trimethylsiloxanyl group. Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n- heptoxy, n-octoxy, 1,1 ,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term "alkylthio group" means the same groups as the alkoxy groups, except that the oxygen atom of ether linkage is replaced by a sulfur atom.

The term "aryl group" is typically C₆-C₂₄aryl, such as phenyl, indenyl, azulenyl, naphthyl, biphenyl, terphenylyl or quadphenylyl, as-indacenyl, s-indacenyl, acenaphthylenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1 -naphthyl, 2-naphthyl,

9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted.

Examples of C₆-C₁₈aryl are phenyl, 1 -naphthyl, 2-naphthyl, 3- or 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, which may be unsubstituted or substituted.

The term "aralkyl group" is typically C₇-C₂₄aralkyl, such as benzyl, 2-benzyl-2-propyl, β- phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl- dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C₇-Ci₂aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted.

The term "aryl ether group" is typically a C_6-24aryloxy group, that is to say O-C_6-24aryl, such as, for example, phenoxy or 4-methoxyphenyl. The term "aryl thioether group" is typically a C_6-24arylthio group, that is to say S-C_&^aryl, such as, for example, phenylthio or 4-methoxyphenylthio. The term "carbamoyl group" is typically a Ci.i₈carbamoyl radical, preferably Ci_-8carbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert- butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The term "cycloalkyl group" is typically C₅-Ci₂cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The term "cycloalkenyl group" means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted. The cycloalkyl group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen and cyano. Examples of such condensed

wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ are independently of each other C₁-C₈-alkyl, C₁-C₈- alkoxy, halogen and cyano, in particular hydrogen.

The wording "a group comprising a five-membered heterocyclic ring, containing one to three heteroatoms selected from the group of nitrogen, oxygen and sulfur" means a single five- membered heterocyclic ring, such as thienyl, furyl, furfuryl, 2H-pyranyl, pyrrolyl, imidazolyl, or pyrazolyl, or a five-membered heterocyclic ring which is part of a fused ring system, which is formed by the five-membered heterocyclic ring with aryl, heteroaryl and/or cycloalkyl groups, which can optionally be substituted. Examples of such groups are contained in the list of groups for A¹ and A² as well as in the definition of heteroaryl or heterocyclic groups.

The wording "a group comprising a six-membered heterocyclic ring, containing one to three heteroatoms selected from the group of nitrogen, oxygen and sulfur" means a single six- membered heterocyclic ring, such as pyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, or a six-membered heterocyclic ring which is part of a fused ring system, which is formed by the six-membered heterocyclic ring with aryl, heteroaryl and/or cycloalkyl groups, which can optionally be substituted. Examples of such groups are contained in the list of groups for A¹ and A² as well as in the definition of heteroaryl or heterocyclic group.

The term "heteroaryl or heterocyclic group" is a ring with five to seven ring atoms, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 21-l-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, preferably the above-mentioned mono- or bicyclic heterocyclic radicals.

The terms "aryl" and "alkyl" in alkylamino groups, dialkylamino groups, alkylarylamino groups, arylamino groups and diarγlgroups are typically C₁-C₂₅aI kyl and C₆-C₂₄aryl, respectively.

The above-mentioned groups can be substituted by a C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group.

The present invention relates further to an electroluminescent device having the fluorescent compounds, T-3 to T-10, T-12, T-13, and T-14 to T-17, or the compositions according to the present invention between an anode and a cathode and emitting light by the action of electrical energy.

Typical constitutions of latest organic electroluminescent devices are:

(i) an anode/a hole transporting layer/an electron transporting layer/a cathode, in which the compounds or compositions of the present invention are used either as positive-hole transport compound or composition, which is exploited to form the light emitting and hole transporting layers, or as electron transport compounds or compositions, which can be exploited to form the light-emitting and electron transporting layers,

(ii) an anode/a hole transporting layer/a light-emitting layer/an electron transporting layer/a cathode, in which the compounds or compositions form the light-emitting layer regardless of whether they exhibit positive-hole or electron transport properties in this constitution, (iii) an anode/a hole injection layer /a hole transporting layer/a light-emitting layer/an electron transporting layer/a cathode, (iv) an anode/a hole transporting layer/a light-emitting layer/ a hole-blocking layer / an electron transporting layer/a cathode,

(v) an anode/a hole injection layer/a hole transporting layer/a light-emitting layer/ a hole- blocking layer /an electron transporting layer/a cathode, (vi) an anode/a light-emitting layer/an electron transporting layer/a cathode,

(vii) an anode/a light-emitting layer/a hole-blocking layer /an electron transporting layer/a cathode,

(viii) a mono-layer containing a light emitting material alone or a combination a light emitting material and any of materials of the hole transporting layer, the hole-blocking layer and/or the electron transporting layer, and

(ix) a multi-layered structure described in (ii) to (vii), wherein a light emitting layer is the mono-layer defined in (viii).

The compounds and compositions of the present invention can, in principal be used for any organic layer, such as, for example, hole transporting layer, light emitting layer, or electron transporting layer, but are preferably used as the light emitting material in the light emitting layer.

In a further embodiment the present invention relates to compositions comprising a guest chromophore and a host chromophore, wherein the absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore, wherein the host chromophore is a diketopyrrolopyrrole having a photoluminescence emission peak at 350 to 500 nm, preferably 400 to 470 nm, most preferred 420 to 450 nm, wherein the host and/or the guest chromophore is a compound of formula I, II, or III.

Accordingly, the compositions comprise a host chromophore of formula I, II, or III or a guest chromophore of formula I, II, or III; or a host chromophore of formula I, II, or III and a guest chromophore of formula I, II, or III.

In addition, the compounds of formula I, II, or III can be used with other known fluorescent compounds as host or guest compounds, for example: Host:

Guest:

The weight ratio of the host chromophore to the guest chromophore is in general 50:50 to 99.99:0.01 , preferably 90:10 to 99.99:0.01, more preferably 95:5 to 99.9:0.1, most preferred 98:2 to 99.9:0.1.

Thin film type electroluminescent devices usually consist essentially of a pair of electrodes and at least one charge transporting layer in between. Usually two charge transporting layers, a hole transporting layer (next to the anode) and an electron transporting layer (next to the cathode) are present. Either one of them contains - depending on its properties as hole-transporting or electron-transporting material - an inorganic or organic fluorescence substance as light-emitting material. It is also common, that a light-emitting material is used as an additional layer between the hole-transporting and the electron-transporting layer. In the above mentioned device structure, a hole injection layer can be constructed between an anode and a hole transporting layer and/or a positive hole inhibiting layer can be constructed between a light emitting layer and an electron transporting layer to maximise hole and electron population in the light emitting layer, reaching large efficiency in charge recombination and intensive light emission.

The devices can be prepared in several ways. Usually, vacuum evaporation is used for the preparation. Preferably, the organic layers are laminated in the above order on a commercially available indium-tin-oxide ("ITO") glass substrate held at room temperature, which works as the anode in the above constitutions. The membrane thickness is preferably in the range of 1 to 10,000 nm, more preferably 1 to 5,000 nm, more preferably 1 to 1 ,000 nm, more preferably 1 to 500 nm. The cathode metal, such as a Mg/Ag alloy, a binary Li-Al or LiF-AI system with an thickness in the range of 50-200 nm is laminated on the top of the organic layers. The vacuum during the deposition is preferably less than 0.1333 Pa (1x 10^~3 Torr), more preferably less than 1.333x 10^~3 Pa (1x 10^~5 Torr), more preferably less than 1.333x 10^"4 Pa (1x 10^"6 Torr).

As anode usual anode materials which possess high work function such as metals like gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten and the like, metallic alloys such as magnesium/copper, magnesium/silver, magnesium/aluminum, aluminum/indium and the like, semiconductors such as Si, Ge, GaAs and the like, metallic oxides such as indium-tin-oxide ("ITO"), ZnO and the like, metallic compounds such as CuI and the like, and furthermore, electroconducting polymers such polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene and the like, preferably ITO, most preferably ITO on glass as substrate can be used. Of these electrode materials, metals, metallic alloys, metallic oxides and metallic compounds can be transformed into electrodes, for example, by means of the sputtering method. In the case of using a metal or a metallic alloy as a material for an electrode, the electrode can be formed also by the vacuum deposition method. In the case of using a metal or a metallic alloy as a material forming an electrode, the electrode can be formed, furthermore, by the chemical plating method (see for example, Handbook of Electrochemistry, pp 383-387, Mazuren, 1985). In the case of using an electroconducting polymer, an electrode can be made by forming it into a film by means of anodic oxidation polymerization method onto a substrate which is previously provided with an electroconducting coating. The thickness of an electrode to be formed on a substrate is not limited to a particular value, but, when the substrate is used as a light emitting plane, the thickness of the electrode is preferably within the range of from 1 nm to 300 nm, more preferably, within the range of from 5 to 200 nm so as to ensure transparency.

In a preferred embodiment ITO is used on a substrate having an ITO film thickness in the range of from 10 nm (100 A) to 1 μ (10000 A), preferably from 20 nm (200 A) to 500 nm (5000 A). Generally, the sheet resistance of the ITO film is chosen in the range of not more than 100 Ω/cm², preferably not more than 50 Ω/cm².

Such anodes are commercially available from Japanese manufacturers, such as Geomatech Co. Ltd., Sanyo Vacuum Co. Ltd., Nippon Sheet Glass Co. Ltd.

As substrate either an electronconducting or electrically insulating material can be used. In case of using an electroconducting substrate, a light emitting layer or a positive hole transporting layer is directly formed thereupon, while in case of using an electrically insulating substrate, an electrode is firstly formed thereupon and then a light emitting layer or a positive hole transporting layer is superposed.

The substrate may be either transparent, semi-transparent or opaque. However, in case of using a substrate as an indicating plane, the substrate must be transparent or semi- transparent.

Transparent electrically insulating substrates are, for example, inorganic compounds such as glass, quartz and the like, organic polymeric compounds such as polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinylchloride, polyvinylalcohol, polyvinylacetate and the like. Each of these substrates can be transformed into a transparent electroconducting substrate by providing it with an electrode according to one of the methods described above.

Examples of semi-transparent electrically insulating substrates are inorganic compounds such as alumina, YSZ (yttrium stabilized zirconia) and the like, organic polymeric compounds such as polyethylene, polypropylene, polystyrene, epoxy resins and the like. Each of these substrates can be transformed into a semi-transparent electroconducting substrate by providing it with an electrode according to one of the abovementioned methods. Examples of opaque electroconducting substrates are metals such as aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold, platinum and the like, various elctroplated metals, metallic alloys such as bronze, stainless steel and the like, semiconductors such as Si, Ge, GaAs, and the like, electroconducting polymers such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyparaphenylene and the like.

A substrate can be obtained by forming one of the above listed substrate materials to a desired dimension. It is preferred that the substrate has a smooth surface. Even, if it has a rough surface, it will not cause any problem for practical use, provided that it has round unevenness having a curvature of not less than 20 μm. As for the thickness of the substrate, there is no restriction as far as it ensures sufficient mechanical strength.

As cathode usual cathode materials which possess low work function such as alkali metals, earth alkaline metals, group 13 elements, silver, and copper as well as alloys or mixtures thereof such as sodium, lithium, potassium, calcium, lithium fluoride (LiF), sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-copper alloy, magnesium-aluminum alloy, magnesium-indium alloy, aluminum, aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium, calcium, and materials exemplified in EP-A 499,011 such as electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline, polyacetylene etc., preferably Mg/Ag alloys, LiF-AI or Li-Al compositions can be used.

In a preferred embodiment a magnesium-silver alloy or a mixture of magnesium and silver, or a lithium-aluminum alloy, lithium fluoride-aluminum alloy or a mixture of lithium and aluminum can be used in a film thickness in the range of from 10 nm (100 A) to 1 μm (10000 A), preferably from 20 nm (200 A) to 500 nm (5000 A).

Such cathodes can be deposited on the foregoing electron transporting layer by known vacuum deposition techniques described above.

In a preferred ambodiment of this invention a light-emitting layer can be used between the hole transporting layer and the electron transporting layer. Usually the light-emitting layer is prepared by forming a thin film on the hole transporting layer.

The organic EL device of the present invention may comprise an inorganic compound layer between at least one of the electrodes and the above organic thin layer. Examples of the inorganic compound used for the inorganic compound layer include various types of oxides, nitrides and oxide nitrides such as alkali metal oxides, alkaline earth metal oxides, rare earth oxides, alkali metal halides, alkaline earth metal halides, rare earth halides, SiO_x, AIO_x, SiN_x, SiON, AION, GeO_x, LiO_x, LiON, TiO_x, TiON, TaO_x, TaON, TaN_x and C. In particular, as the component contacting the anode, SiO_x, AIO_x, SiN_x, SiON, AION, GeO_x and C are preferable, since a suitable interface layer of injection is formed. As the component contacting the cathode LiF, MgF₂, CaF₂ and NaF are preferable.

As methods for forming said thin film, there are, for example, the vacuum deposition method, the spin-coating method, the casting method, the Langmuir-Blodgett ("LB") method and the like. Among these methods, the vacuum deposition method, the spin-coating method and the casting method are particularly preferred in view of ease of operation and cost.

In case of forming a thin film using a composition by means of the vacuum deposition method, the conditions under which the vacuum deposition is carried out are usually strongly dependent on the properties, shape and crystalline state of the compound(s). However, optimum conditions are usually as follows: temperature of the heating boat: 100 to 400⁰C; substrate temperature: -100 to 350⁰C; pressure: 1.33x10⁴ Pa (1x10² Torr) to 1.33x10^"4 Pa (1x10⁶ Torr) and deposition rate: 1 pm to 6 nm/sec.

In an organic EL element, the thickness of the light emitting layer is one of the factors determining its light emission properties. For example, if a light emitting layer is not sufficiently thick, a short circuit can occur quite easily between two electrodes sandwiching said light emitting layer, and therefore, no EL emission is obtained. On the other hand, if the light emitting layer is excessively thick, a large potential drop occurs inside the light emitting layer because of its high electrical resistance, so that the threshold voltage for EL emission increases. Accordingly, the thickness of the organic light emitting layer is limited to the range of from 5 nm to 5 μm, preferably to the range of from 10 nm to 500 nm.

In the case of forming a light emitting layer by using the spin-coating method and the casting method, ink jet printing method, the coating can be carried out using a solution prepared by dissolving the composition in a concentration of from 0.0001 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide, dichloromethane, dimethylsulfoxide and the like. If the concentration exceeds 90% by weight, the solution usually is so viscous that it no longer permits forming a smooth and homogenous film. On the other hand, if the concentration is less than 0.0001 % by weight, the efficiency of forming a film is too low to be economical. Accordingly, a preferred concentration of the composition is within the range of from 0.01 to 80% by weight.

In the case of using the above spin-coating or casting method, it is possible to further improve the homogeneity and mechanical strength of the resulting layer by adding a polymer binder to the solution for forming the light emitting layer. In principle, any polymer binder may be used, provided that it is soluble in the solvent in which the composition is dissolved. Examples of such polymer binders are polycarbonate, polyvinylalcohol, polymethacrylate, polymethylmethacrylate, polyester, polyvinylacetate, epoxy resin and the like. However, if the solid content composed of the polymer binder and the composition exceeds 99% by weight, the fluidity of the solution is usually so low that it is impossible to form a light emitting layer excellent in homogeneity. On the other hand, if the content of the composition is substantially smaller than that of the polymer binder, the electrical resistance of said layer is very large, so that it does not emit light unless a high voltage is applied thereto. Accordingly, the preferred ratio of the polymer binder to the composition is chosen within the range of from 10:1 to 1 :50 by weight, and the solid content composed of both components in the solution is preferably within the range of from 0.01 to 80% by weight, and more preferably, within the range of 0.1 to 60% by weight.

As hole-transporting layers known organic hole transporting compounds such as polyvinyl carbazole

a TPD compound disclosed in J. Amer. Chem. Soc. 90 (1968) 3925:

wherein Q₁ and Q₂ each represent a hydrogen atom or a methyl group; a compound disclosed in J. Appl. Phys. 65(9) (1989) 3610:

a stilbene based compound

wherein T and T₁ stand for an organic radical; a hydrazone based compound

wherein R_x, R_y and R_z stand for an organic radical, and the like can be used.

Compounds to be used as a positive hole transporting material are not restricted to the above listed compounds. Any compound having a property of transporting positive holes can be used as a positive hole transporting material such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivative, pyrazolone derivatives, phenylene diamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxazole derivatives, stilbenylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, copolymers of aniline derivatives, PEDOT (poly(3,4-ethylenedioxy-thiophene)) or PEDOT-PSS (poly(3,4- ethylenedioxy-thiophene)-poly(styrenesulfonate)) and the derivatives thereof, electro- conductive oligomers, particularly thiophene oligomers, porphyrin compounds, aromatic tertiary amine compounds, stilbenyl amine compounds etc. Particularly, aromatic tertiary amine compounds such as N,N,N',N'-tetraphenyl-4,4'- diaminobiphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)- 4,4'-diaminobiphenyl (TPD), 2,2'- bis(di-p-torylaminophenyl)propane, 1 ,1'-bis(4-di-torylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenyl- methane, N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N, N₁N', N'- tetraphenyl-4,4'-diaminodiphenylether, 4,4'-bis(diphenylamino)quaterphenyl, N,N,N-tri(p- tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)stilyl]stilbene, 4-N,N-diphenylamino-(2- diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbene, N-phenylcarbazole etc. are used.

Furthermore, 4,4'-bis[N-(1-naphtyl)-N-phenylamino]biphenyl disclosed in US-B-5,061 ,569 and the compounds disclosed in EP-A 508,562, in which three triphenylamine units are bound to a nitrogen atom, such as 4,4',4"-tris[N-(3-methylphenyl)-N- phenylamino]triphenylamine, can be used.

A positive hole transporting layer can be formed by preparing an organic film containing at least one positive hole transporting material on the anode. The positive hole transporting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, ink jet printing method, the LB method and the like. Of these methods, the vacuum deposition method, the spin-coating method and the casting method are particularly preferred in view of ease and cost.

In the case of using the vacuum deposition method, the conditions for deposition may be chosen in the same manner as described for the formation of a light emitting layer (see above). If it is desired to form a positive hole transporting layer comprising more than one positive hole transporting material, the coevaporation method can be employed using the desired compounds. In the case of forming a positive hole transporting layer by the spin-coating method or the casting method, the layer can be formed under the conditions described for the formation of the light emitting layer (see above).

As in the case of forming the light emitting layer a smoother and more homogeneous positive hole transporting layer can be formed by using a solution containing a binder and at least one positive hole transporting material. The coating using such a solution can be performed in the same manner as described for the light emitting layer. Any polymer binder may be used, provided that it is soluble in the solvent in which the at least one positive hole transporting material is dissolved. Examples of appropriate polymer binders and of appropriate and preferred concentrations are given above when describing the formation of a light emitting layer.

The thickness of the positive hole transporting layer is preferably chosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more preferably from 2 to 50 nm. As hole injection materials known organic hole transporting compounds such as metal-free phthalocyanine (H₂Pc), copper-phthalocyanine (Cu-Pc) and their derivatives as described, for example, in JP64-7635 can be used. Furthermore, some of the aromatic amines defined as hole transporting materials above, which have a lower ionisation potential than the hole transporting layer, can be used.

A hole injection layer can be formed by preparing an organic film containing at least one hole injection material between the anode layer and the hole transporting layer. The hole injection layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, the LB method and the like. The thickness of the layer is preferably from 5 nm to 5 μm, and more preferably from 10 nm to 100 nm.

The electron transporting materials should have a high electron injection efficiency (from the cathode) and a high electron mobility. The following materials can be exemplified for electron transporting materials: tris(δ-hydroxyquinolinato)-aluminum(lll) and its derivatives, bis(10- hydroxybenzo[h]quinolinolato)berγllium(ll) and its derivatives, oxadiazole derivatives, such as 2-(4-biphenyl)-5-(4-tert.-butylphenyl)-1,3,4-oxadiazole and its dimer systems, such as 1,3- bis(4-tert.-butylphenyl-1 ,3,4)oxadiazolyl)biphenylene and 1 ,3-bis(4-tert.-butylphenyl-1 ,3,4- oxadiazolyl)phenylene, dioxazole derivatives, triazole derivatives, coumarine derivatives, imidazopyridine derivatives, phenanthroline derivatives or perylene tetracarboxylic acid derivatives disclosed in Appl. Phys. Lett. 48 (2) (1986) 183.

Other suitable compounds for the electron transporting material are hetero-cyclic compounds such as, benzimidazole derivatives, benzoxazole derivatives, thiadiazole derivative, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, oligo- pyridine derivatives, e.g. bipyridine derivatives and terpyridine derivatives, naphthylidine derivatives, indole derivatives and naphthalimide derivatives; silole derivatives; and phosphineoxide derivatives.

It is possible to add a reducing dopant to the electron transporting layer to improve the EL device property. The reducing dopant is a material that can reduce the electron transporting material. Examples of the reducing dopant are alkaline metals, e.g. Na, K, Rb and Cs, and alkali earth metals, e.g. Ca, Sr and Ba.

An electron transporting layer can be formed by preparing an organic film containing at least one electron transporting material on the hole transporting layer or on the light-emitting layer. The electron transporting layer can be formed by the vacuum deposition method, the spin- coating method, the casting method, the LB method and the like.

It is preferred that the positive hole inhibiting materials for a positive hole inhibiting layer have high electron injection/transporting efficiency from the electron transporting layer to the light emission layer and also have higher ionisation potential than the light emitting layer to prevent the flowing out of positive holes from the light emitting layer to avoid a drop in luminescence efficiency.

As the positive hole inhibiting material known materials, such as BaIq, TAZ and phenanthroline derivatives, e.g. bathocuproine (BCP), can be used:

BCP BaIq TAZ

The positive hole inhibiting layer can be formed by preparing an organic film containing at least one positive hole inhibiting material between the electron transporting layer and the light-emitting layer. The positive hole inhibiting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, ink jet printing method, the LB method and the like. The thickness of the layer preferably is chosen within the range of from 5 nm to 2 μm, and more preferably, within the range of from 10 nm to 100 nm.

As in the case of forming a light emitting layer or a positive hole transporting layer, a smoother and more homogeneous electron transporting layer can be formed by using a solution containing a binder and at least one electron transporting material.

The thickness of an electron transporting layer is preferably chosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more preferably from 2 to 50 nm. The property of charge injection can be improved by adding an electron-accepting compound to the hole injection layer and/or the hole transporting layer and an electron-donating material to the electron transporting layer.

In general, the host chromphore is a compound having a photoluminescence emission peak at 350 to 500 nm, preferably 400 to 470 nm, most preferred 420 to 450 nm.

The light-emitting compositions have a fluorescence emission maximum in the range of from 400 to 500, preferably from 420 to 480, more preferred from 440 to 460 nm. Further, the inventive compounds preferably exhibit an absorption maximum in the range of 300 to 460 nm.

The light-emitting compositions usually exhibit a fluorescence quantum yield ("FQY") in the range of from 1 > FQY > 0.3 (measured in aerated toluene or DMF). Further, in general, the inventive compositions exhibit a molar absorption coefficient in the range of from 5000 to 100000.

Another embodiment of the present invention relates to a method of coloring high molecular weight organic materials (having a molecular weight usually in the range of from 10³ to 10⁷ g/mol; comprising biopolymers, and plastic materials, including fibres) by incorporating therein the inventive compounds or compositions by methods known in the art.

The inventive compounds and compositions can be used, as described for the DPP compounds of formula T in EP-A-1087005, for the preparation of inks, for printing inks in printing processes, for flexographic printing, screen printing, packaging printing, security ink printing, intaglio printing or offset printing, for pre-press stages and for textile printing, for office, home applications or graphics applications, such as for paper goods, for example, for ballpoint pens, felt tips, fiber tips, card, wood, (wood) stains, metal, inking pads or inks for impact printing processes (with impact-pressure ink ribbons), for the preparation of colorants, for coating materials, for industrial or commercial use, for textile decoration and industrial marking, for roller coatings or powder coatings or for automotive finishes, for high-solids (low-solvent), water-containing or metallic coating materials or for pigmented formulations for aqueous paints, for the preparation of pigmented plastics for coatings, fibers, platters or mold carriers, for the preparation of non-impact-printing material for digital printing, for the thermal wax transfer printing process, the ink jet printing process or for the thermal transfer printing process, and also for the preparation of color filters, especially for visible light in the range from 400 to 700 nm, for liquid-crystal displays (LCDs) or charge combined devices (CCDs) or for the preparation of cosmetics or for the preparation of polymeric ink particles, toners, dye lasers, dry copy toners liquid copy toners, or electrophotographic toners, and electroluminescent devices.

Another preferred embodiment concerns the use of the inventive compounds and compositions for color changing media. There are three major techniques in order to realize full-color organic electroluminescent devices:

(i) use of the three primary colors blue, green and red generated by electroluminescence, (ii) conversion of the electroluminescent blue or white to photoluminescent green and red via color changing media (CCM), which absorb the above electroluminescent blue, and fluorescence in green and red. (iii) conversion of the white luminescent emission to blue, green and red via color filters.

The inventive compounds or compositions are useful for EL materials for the above category (i) and, in addition, for the above mention technique (ii).

The inventive compounds or compositions are useful for EL materials for the above category (iii) as an element of white luminescent in combination of other compensatory electroluminescence to construct white luminescent.

Illustrative examples of suitable organic materials of high molecular weight which can be colored with the inventive compositions are described in EP-A-1087005.

Particularly preferred high molecular weight organic materials, in particular for the preparation of a paint system, a printing ink or ink, are, for example, cellulose ethers and esters, e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins (polymerization or condensation resins) such as aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, poly- urethanes, polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone and silicone resins as well as their possible mixtures with one another. It is also possible to use high molecular weight organic materials in dissolved form as film formers, for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.

Said high molecular weight organic materials may be obtained singly or in admixture, for example in the form of granules, plastic materials, melts or in the form of solutions, in particular for the preparation of spinning solutions, paint systems, coating materials, inks or printing inks.

In a particularly preferred embodiment of this invention, the inventive compounds and compositions are used for the mass coloration of polyvinyl chloride, polyamides and, especially, polyolefins such as polyethylene and polypropylene as well as for the preparation of paint systems, including powder coatings, inks, printing inks, color filters and coating colors.

Illustrative examples of preferred binders for paint systems are alkyd/melamine resin paints, acryl/melamine resin paints, cellulose acetate/cellulose butyrate paints and two-pack system lacquers based on acrylic resins which are crosslinkable with polyisocyanate.

Hence, another embodiment of the present invention relates to a composition comprising (a) 0.01 to 50, preferably 0.01 to 5, particularly preferred 0.01 to 2% by weight, based on the total weight of the coloured high molecular organic material, of a fluorescent compound or of a composition according to the present invention, and (b) 99.99 to 50, preferably 99.99 to 95, particularly preferred 99.99 to 98% by weight, based on the total weight of the coloured high molecular organic material, of a high molecular organic material, and (c) optionally, customary additives such as rheology improvers, dispersants, fillers, paint auxiliaries, siccatives, plasticizers, UV-stabilizers, and/or additional pigments or corresponding precursors in effective amounts, such as e.g. from 0 to 50% by weight, based on the total weight of (a) and (b).

To obtain different shades, the inventive fluorescent DPP compounds of formula I or the inventive compositions may advantageously be used in admixture with fillers, transparent and opaque white, colored and/or black pigments as well as customary luster pigments in the desired amount. For the preparation of paints systems, coating materials, color filters, inks and printing inks, the corresponding high molecular weight organic materials, such as binders, synthetic resin dispersions etc. and the inventive compounds or compositions are usually dispersed or dissolved together, if desired together with customary additives such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents. This can be achieved by dispersing or dissolving the individual components by themselves, or also several components together, and only then bringing all components together, or by adding everything together at once.

Hence, the present invention relates also to a method of coloring a high molecular weight organic material by incorporating therein the inventive compounds or compositions by known methods in the art.

Hence, a further embodiment of the present invention relates to a method of using the inventive compounds or compositions for the preparation of dispersions and the corresponding dispersions, and paint systems, coating materials, color filters, inks and printing inks comprising the inventive compositions.

A particularly preferred embodiment relates to the use of the inventive compounds or compositions for the preparation of fluorescent tracers for e.g. leak detection of fluids such as lubricants, cooling systems etc., as well as to fluorescent tracers or lubricants comprising the inventive compositions.

For the pigmentation of high molecular weight organic material, the inventive compounds or compositions, optionally in the form of masterbatches, are mixed with the high molecular weight organic materials using roll mills, mixing apparatus or grinding apparatus. Generally, the pigmented material is subsequently brought into the desired final form by conventional processes, such as calandering, compression molding, extrusion, spreading, casting or injection molding.

For pigmenting lacquers, coating materials and printing inks the high molecular weight organic materials and the inventive compounds or compositions, alone or together with additives, such as fillers, other pigments, siccatives or plasticizers, are generally dissolved or dispersed in a common organic solvent or solvent mixture. In this case it is possible to adopt a procedure whereby the individual components are dispersed or dissolved individually or else two or more are dispersed or dissolved together and only then are all of the components combined.

The present invention additionally relates to inks comprising a coloristically effective amount of the pigment dispersion of the inventive compositions.

The weight ratio of the pigment dispersion to the ink in general is chosen in the range of from 0.001 to 75% by weight, preferably from 0.01 to 50% by weight, based on the overall weight of the ink.

The preparation and use of color filters or color-pigmented high molecular weight organic materials are well-known in the art and described e.g. in Displays 14/2, 1151 (1993), EP-A 784085, or GB-A 2,310,072.

The color filters can be coated for example using inks, especially printing inks, which can comprise pigment dispersions comprising the inventive compositions or can be prepared, for example, by mixing a pigment dispersion comprising an inventive composition with chemically, thermally or photolytically structurable high molecular weight organic material (so-called resist). The subsequent preparation can be carried out, for example, in analogy to EP-A 654 711 by application to a substrate, such as a LCD (liquid crystal display), subsequent photostructuring and development.

Particular preference for the production of color filters is given to pigment dispersions comprising an inventive compound or composition which possess non-aqueous solvents or dispersion media for polymers. The present invention relates, moreover, to toners comprising a pigment dispersion containing an inventive compound or composition or a high molecular weight organic material pigmented with an inventive composition in a coloristically effective amount. The present invention additionally relates to colorants, colored plastics, polymeric ink particles, or non-impact-printing material comprising an inventive composition, preferably in the form of a dispersion, or a high molecular weight organic material pigmented with an inventive composition in a coloristically effective amount.

A coloristically effective amount of the pigment dispersion according to this invention comprising an inventive composition denotes in general from 0.0001 to 99.99% by weight, preferably from 0.001 to 50% by weight and, with particular preference, from 0.01 to 50% by weight, based on the overall weight of the material pigmented therewith. The inventive compositions can be applied to colour polyamides, because they do not decompose during the incorporation into the polyamides. Further, they exhibit an exceptionally good lightfastness, a superior heat stability, especially in plastics.

The organic EL device of the present invention has significant industrial values since it can be adapted for a flat panel display of an on-wall television set, a flat light-emitting device, a light source for a copying machine or a printer, a light source for a liquid crystal display or counter, a display signboard and a signal light. The compounds and compositions of the present invention can be used in the fields of an organic EL device, an electrophotographic photoreceptor, a photoelectric converter, a solar cell, an image sensor, and the like.

Claims

1. A fluorescent compound of the formula

(l), or (II), (III), wherein

X = O, -N-R¹ and Y = O, -N-R², wherein R¹ and R² may be the same or different and are selected from a C₁-C₂₅alkyl group, which can optionally be interrupted by one or more oxygen atoms and/or can optionally be substituted by a hydroxyl group, an alkoxy group or an amino group; an allyl group, which can be substituted one to three times with C₁-C₃alkyl, a cycloalkyl group, which can optionally be substituted one to three times with C₁-C₈alkyl and/or C₁- C₈alkoxy, a cycloalkyl group, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; an alkenyl group, a cycloalkenyl group, an alkynyl group, a heterocyclic group, haloalkyl, haloalkenyl, haloalkynyl, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, aryl, heteroaryl, or -CR³R⁴-(CH₂)_m-A³ wherein R³ and R⁴ independently from each other stand for hydrogen or C₁-C₄alkyl, or phenyl which can be substituted one to three times with C₁-C₃alkyl, A³ stands for aryl, or heteroaryl, in particular phenyl or 1- or 2-naphthyl which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and m stands for 0, 1 , 2, 3 or 4,

A¹, A³ and A⁵ stand independently of each other for hydrogen, cycloalkyl, especially cyclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or phenyl groups, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; 2-adamantyl, or 1-

adamantyl, alkynyl; , or , wherein m is as defined above, R⁵, R⁶, R⁷, R⁵, R⁶ and R⁷ may be the same or different and are selected from hydrogen, C₁-C₂₅alkyl, which optionally can be substituted by ahydroxyl group, an alkoxy group, an amino group, a heterocyclic group, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, aryl, or heteroarγl; cycloalkyl, especially cyclohexyl, which can optionally be substituted by one, or two C₁- C₈alkyl groups, or C₆-Ci₄aryl groups, especially phenyl, or naphthyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cycloalkyl, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; 2-adamantyl, or 1-adamantyl; aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, heteroaryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carboxyl group, an ester group, a carbamoyl group, an amino group, which can optionally be substituted by an alkyl group, alkylaryl group, an aryl group, a heteroaryl group, an heterocyclic group, or an aralkyl group, or two substituents on the nitrogen atom together with the nitrogen atom to which they are bonded form a five or six membered heterocyclic ring; a nitro group, a silyl group, or a siloxanyl group;

A², A⁴ and A⁶ stand independently of each other for A¹, an unsubstituted, or substituted aryl group, or a unsubstituted, or substituted heteroaryl group. A⁷ isalkylene, alkenylene, alkynylene, allylene, arylene, or heteroarylene, which is optionally substituted one to three times with C₁-C₈-alkyl, or C₁-C₈-alkoxy, with the proviso that the following compound of formula I is excluded, wherein X and Y are N-R¹ and N-R², respectively:

2. The fluorescent compound according to claim 1, wherein R¹ and R² independently from each other stand for C₁-C₈alkyl, C₅-Ci₂-cycloalkyl, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, or -CR³R⁴-(CH₂)_m- A³, wherein R³ and R⁴ stand for hydrogen, or C₁-C₄alkyl, A³ stands for phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C₁-C₈alkyl and/or C₁- C₈alkoxy, and m stands for 0 or 1.

3. The compound of formula Il according to claim 1, wherein A⁷ is a single bond, -CO-,

, or , wherein n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1 to 3, n8 is an integer of l to 10,

A⁶ and A⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E' and/or interrupted by D', C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by

G', C₂-C₂oheteroaryl, C₂-C₂oheteroaryl which is substituted by G', C₂-C₁₈alkenyl, C₂- C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E' and/or interrupted by

D', C₇-C₂₅aralkyl, or -CO-A²⁸,

A⁹ and A¹⁰ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E' and/or interrupted by D', C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G', C₂-

C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G', C₂-Ci ₈alkenyl, C₂-Ci ₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E' and/or interrupted by D', or C₇- C₂₅aralkyl, or

A⁹ and A¹⁰ form a ring, especially a five- or six-membered ring, which can optionally be substituted by one or more C₁-C₁₈alkyl groups;

A¹⁴ and A¹⁵ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E' and/or interrupted by D', C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G', C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G',

D' is -CO-; -COO-; -S-; -SO-; -SO₂-; -O-; -NA²⁵-; -SiA³⁰A³¹-; -POA³²-; -CA²³=CA²⁴-; or -

C≡C-; and

E' is -OA²⁹; -SA²⁹; -NA²⁵A²⁶; -COA²⁸; -COOA²⁷; -CONA²⁵A²⁶; -CN; -OCOOA²⁷; or halogen; G' is E', or C₁-C₁₈alkyl; wherein A²³, A²⁴, A²⁵ and A²⁶ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁- C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by -O-; or A²⁵ and A²⁶

together form a five or six membered ring, in particular

A²⁷ and A²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by -O-,

A²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-

C18alkyl; or C₁-C₁₈alkyl which is interrupted by -O-,

A³⁰ and A³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and

A³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl.

The fluorescent compound according to claim 1 , wherein the compound is a compound of formula

wherein

R¹ and R² independently from each other stand for C₁-C₈alkyl, C₅-Ci₂-cycloalkyl, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C₁-C₈alkyl and/or C₁- C₈alkoxy, or -CR³R⁴-(CH₂)_m-A^3', wherein R³ and R⁴ stand for hydrogen, or C₁-C₄alkyl, A³ stands for phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and m stands for 0 or 1 ,

A¹, A³ and A⁵ stand independently of each other for C₁-C₂₅alkyl, cyclohexyl, which can optionally be substituted by one, or two C₁-C₈alkyl groups, or phenyl, 1-naphthyl and/or 2-naphthyl groups, which can optionally be substituted by one, or two C₁-C₈alkyl groups, cyclohexyl, which is condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen, nitro, or cyano; or 1-adamantyl; A², A⁴ and A⁶ stand independently of each other for A¹, or A², A⁴ and A⁶ stand independently of each other for

, wherein X is N, or C-R⁸,

R⁵ to R¹¹ may be the same or different and are selected from hydrogen, C₁-C₂₅alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an arγl ether group, an aryl thioether group, aryl, heteroarγl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR²⁷R²⁸, wherein R²⁷ and R²⁸ independently of each other stand for a hydrogen atom, an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted arγl group, an optionally substituted heteroarγl group, an optionally substituted heterocyclic group, an aralkγl group, or R j27 and R j28 together with the nitrogen atom to which theγ are bonded form a five or six membered heterocyclic ring, which can be condensed by one or two optionally substituted phenyl groups, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, or at least two adjacent substituents R⁵ to R¹¹ form an aromatic, heteroaromatic, or aliphatic fused ring system, or A², A⁴ and A⁶ stand independently of each other for

wherein R¹⁰¹ to R¹²³ may be the same or different and are selected from hydrogen, C₁- C₂₅alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR²⁷R²⁸, wherein R²⁷ and R²⁸ are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, or at least two adjacent substituents R¹¹⁵ to R¹²¹ form an aromatic, heteroaromatic or aliphatic fused ring system,

R¹²⁴ and R¹²⁵ may be the same or different and are selected from C₁-C₁₈alkyl; C₁- C₁₈alkoxy, A³, C₆-C₁₈aryl; C₇-Ci ₈aralkyl; or R¹²⁴ and R¹²⁵ together form a ring especially a five-, six- or seven-membered ring, which can optionally be substituted by C₁-C₈alkyl, or which can optionally be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano; or A², A⁴ and A⁶ stand independently of each other for

R and R are independently of each other a hydrogen atom, a C₁-C₁₈alkyl group, a

C₁-C₁₈alkoxy group, a group of formula

, or

, wherein R³¹⁸, R³¹⁹ and R³²⁰ independently from each other stand for hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl, and

R³¹⁷ stands for is a hydrogen atom, a C₁-C₂₅alkyl group, which might be interrupted by - O-, a cycloalkyl group, a C₇-C₁₈aralkyl group, a C₆-C₁₈aryl group, or a heterocyclic group, which may be substituted by G; wherein G is C₁-C₁₈alkyl, -OR³²⁵, -SR³²⁵, -NR³²⁵R³²⁶, -COR³²⁸, -COOR³²⁷, -OCOOR³²⁷, -CONR³²⁵R³²⁶, -CN, or halogen; wherein R³²⁵ and R³²⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by -O-; or

R³²⁵ and R³²⁶ together form a five or six membered ring, in particular

R³²⁸ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁- C₁₈alkyl; C₇-Ci₂alkylaryl, or C₁-C₁₈alkyl which is interrupted by -O-; or

wherein R¹³¹ to R¹⁵² may be the same or different and are selected from hydrogen, C₁- C₂₅alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR²⁷R²⁸, wherein R²⁷ and R²⁸ are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, R is a hydrogen atom, a C₁-C₂₅alkyl group, which might be interrupted by -O-, a cycloalkyl group, an aralkyl group, an arγl group, or a heterocyclic group, and A⁷ is a group of formula

, wherein A⁸ is C₁-C₁₈alkyl,

A⁹ and A¹⁰ are independently of each other C₁-C₁₈alkyl, or A⁹ and A¹⁰ form a ring, especially a five- or six-membered ring, which can optionally be substituted by C₁- C₈alkyl, or C₁-C₈alkoxy,

A¹⁴ and A¹⁵ are independently of each other H, or C₁-C₈alkyl, and A⁶ and A⁷ are independently of each other H, C₁-C₈alkyl, or C₁-C₈alkoxy.

5. The fluorescent compound according to claim 4:

6. A composition, comprising a fluorescent compound according to any of claims 1 to 5.

7. An electroluminescent device, comprising a fluorescent compound according to any of claims 1 to 5, including compounds T-13, T-15, T-16 and T-17, or a composition according to claim 6.

8. A composition of a high molecular weight organic material, comprising

(a) 0.01 to 50% by weight, based on the total weight of the colored high molecular weight organic material, of the fluorescent compound according to any of claims 1 to 5, or the composition of claim 6, and

(b) 99.99 to 50% by weight, based on the total weight of the colored high molecular weight organic material, of a high molecular organic material, and

(c) optionally, customary additives in effective amounts.

9. Use of the fluorescent compounds according to any of claims 1 to 5, or the composition of claim 6 for the preparation of inks, colorants, pigmented plastics for coatings, nonimpact-printing material, color filters, cosmetics, or for the preparation of polymeric ink particles, toners, as fluorescent tracers, in color changing media, in solid dye laser, EL laser and electroluminescent device.

10. Compounds of formula

(l), or (II), (III), wherein

X and Y are -NH, and

A¹, A², A³, A⁴, A⁷, A⁵ and A⁶ are as defined in claim 1, with the proviso that the following compounds of formula I are excluded:

ula III is excluded, wherein X and Y are NH: