WO1992015099A1 - Molecular-electronic devices - Google Patents

Molecular-electronic devices Download PDF

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Publication number
WO1992015099A1
WO1992015099A1 PCT/GB1992/000338 GB9200338W WO9215099A1 WO 1992015099 A1 WO1992015099 A1 WO 1992015099A1 GB 9200338 W GB9200338 W GB 9200338W WO 9215099 A1 WO9215099 A1 WO 9215099A1
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Prior art keywords
macrocyclic compound
macrocyclic
porphyrin
substituents
compound
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Application number
PCT/GB1992/000338
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French (fr)
Inventor
Lionel Robert Milgrom
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British Technology Group Plc
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Publication date
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Priority to JP4505053A priority Critical patent/JPH06503204A/en
Publication of WO1992015099A1 publication Critical patent/WO1992015099A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances

Definitions

  • MOLECULAR-ELECTRONIC DEVICES This invention relates to novel molecular-electronic devices which comprise conducting species; to processes for the production of the conducting species and to certain novel conducting compounds.
  • One class of compounds which have been proposed as having potentially valuable conduction properties are macrocyclic compounds which are capable of forming columnar stacks in the solid state.
  • macrocyclic compounds which are capable of forming columnar stacks in the solid state.
  • examples of such compounds include phthalocyanines and porphyrins.
  • the formation of metal complexes of such compounds or the introduction of suitable dopants has been found to enhance the conduction properties of these compounds.
  • These prior proposals have all been directed to compounds wherein the mode of conduction is electronic.
  • derivatives of macrocyclic compounds which comprise substituents which are capable of interacting to form a hydrogen bond may exhibit proton conductivity. Furthermore, the bond formation facilitates the formation of ordered molecular stacks and this enhances the ability to form useful conducting materials.
  • this invention provides a molecular-electronic device wherein the conducting material comprises a macrocyclic compound which is capable of forming columnar stacks wherein said compound comprising at least one substituent capable of forming a hydrogen bond as part of its molecular structure.
  • the conducting material is such that the mode of conduction is at least partially that of proton conduction.
  • the derivatives which we have found to be useful are those which contain substituents which facilitate the formation of hydrogen bonds between the molecular layers in the columnar stack. The nature of the substituent groups which are capable of forming such bonds is well known in the art.
  • the preferred derivatives for use according to this invention are those in which at least three and more preferably at least four sites at which hydrogen bonds may be formed are present.
  • substituents are preferably situated symmetrically at different positions on the macrocyclic compounds.
  • the preferred substituents which may be introduced into the macrocyclic compounds in order to form the derivatives useful according to this invention are those which contain at least one hydroxyl , carbox late, primary amine or secondary amine function.
  • a preferred group of macrocyclic compounds from which derivatives useful according to this invention may be prepared are the tetrapyrolic macrocycles especially the porphyrins and the phthalocyanines.
  • R , R , R3 and R which may be the same or different represent a monovalent group comprising a heterocyclic ring comprising at least one nitrogen atom.
  • the preferred compounds are those wherein the substituents R are identical and represent an imidazole pyrimidine or purine group.
  • the most preferred compounds are those in which a nitrogen atom within the heterocyclic ring of the substituent is at the ⁇ position relative to the macrocyclic ring.
  • the most preferred compounds are those wherein the substituents R represent imidazole groups and the most preferred compound is mesotetrakis(2-imidazo1yl) porphyrin.
  • the porphyrins having the Formula I may be prepared by syntheses known in the art.
  • the 1:1 metal complexes of the tetrapyrrolic macrocyclic compounds described above may also exhibit conduction properties and molecular-electronic devices comprising such complexes form a further aspect of this invention.
  • These complexes may be prepared using processes known to be useful in the art.
  • the nickel, palladium and platinum complexes of the porphyrins and phthalocyanines are especially useful and form a preferred aspect of this invention.
  • the ferric iron and cupric copper complexes are also of particular value.
  • the metal complexes may find particular application as a conducting material in molecular-electronic devices since they may exhibit both proton and electronic conduction. Devices wherein the conducting material exhibits this dual conduction capability form another aspect of this invention.
  • Example 1 The invention is illustrated by the following examples.
  • Example 1 The invention is illustrated by the following examples.
  • TIP Mesotetrakis(2-imidazolyl)porphyrin
  • the material could not be chromatographed on silica gel.
  • the IR spectrum of the product shows a broad, intense absorption between 2400 cm -1 and 3600 cm -1 , similar to that shown by imidazole.
  • TIP tetraphenyl porphyrin
  • Compressed discs of TIP and TPP were prepared. These were retained between spring-loaded electrodes composed of Pt black electrochemically deposited on a copper substrate in a vacuum- tight environment, in which the partial pressure of water was closely controlled.
  • TIP was evacuated overnight at 10 -2 torr, to remove bound water. It was then allowed to equilibrate in the test cell with an atmosphere containing water vapour at 11.3% partial pressure. The conductivity of the TIP sample was then measured and found to be 6.8*10 "12 S m ⁇ ⁇ . A pulse of dry hydrogen gas was then admitted to the cell and the conductivity was observed to rise by nearly four orders of magnitude to 2.8*10 -8 S m "1 , demonstrating that conductivity in TIP is protonic and hydration dependant.
  • a saturated aqueous solution of nickel chloride (lO ls) was then added with warming.
  • the UV/visible spectrum showed a collapse of the four banded spectrum to a two banded spectrum after a period of about three hours.
  • the mixture was allowed to cool to ambient temperature then several drops of 0.880 ammonia were added.
  • the 1:1 nickel porphyrin complex precipitated out leaving the excess nickel in solution in the form of its hexammine complex.

Abstract

Derivatives of macrocyclic compounds capable of forming columnar stacks in the solid phase such as porphyrin and phthalocyanines which are capable of forming hydrogen bonds have been found to exhibit enhanced conduction properties. A preferred compound is mesotetrakis(2-imidazolyl)porphyrin. The derivatives may exhibit proton conductance. The 1:1 metal complexes are valuable in so far as they may exhibit both protonic and electronic conduction.

Description

MOLECULAR-ELECTRONIC DEVICES This invention relates to novel molecular-electronic devices which comprise conducting species; to processes for the production of the conducting species and to certain novel conducting compounds.
One class of compounds which have been proposed as having potentially valuable conduction properties are macrocyclic compounds which are capable of forming columnar stacks in the solid state. Examples of such compounds include phthalocyanines and porphyrins. The formation of metal complexes of such compounds or the introduction of suitable dopants has been found to enhance the conduction properties of these compounds. These prior proposals have all been directed to compounds wherein the mode of conduction is electronic.
We have now discovered that derivatives of macrocyclic compounds which comprise substituents which are capable of interacting to form a hydrogen bond may exhibit proton conductivity. Furthermore, the bond formation facilitates the formation of ordered molecular stacks and this enhances the ability to form useful conducting materials.
Accordingly, from one aspect this invention provides a molecular-electronic device wherein the conducting material comprises a macrocyclic compound which is capable of forming columnar stacks wherein said compound comprising at least one substituent capable of forming a hydrogen bond as part of its molecular structure. In a preferred embodiment the conducting material is such that the mode of conduction is at least partially that of proton conduction. The derivatives which we have found to be useful are those which contain substituents which facilitate the formation of hydrogen bonds between the molecular layers in the columnar stack. The nature of the substituent groups which are capable of forming such bonds is well known in the art. The preferred derivatives for use according to this invention are those in which at least three and more preferably at least four sites at which hydrogen bonds may be formed are present. These substituents are preferably situated symmetrically at different positions on the macrocyclic compounds. The preferred substituents which may be introduced into the macrocyclic compounds in order to form the derivatives useful according to this invention are those which contain at least one hydroxyl , carbox late, primary amine or secondary amine function.
A preferred group of macrocyclic compounds from which derivatives useful according to this invention may be prepared are the tetrapyrolic macrocycles especially the porphyrins and the phthalocyanines.
Especially valuable for use are the porphyrins of the Formula I
Figure imgf000004_0001
wherein R , R , R3 and R which may be the same or different represent a monovalent group comprising a heterocyclic ring comprising at least one nitrogen atom. The preferred compounds are those wherein the substituents R are identical and represent an imidazole pyrimidine or purine group. The most preferred compounds are those in which a nitrogen atom within the heterocyclic ring of the substituent is at the β position relative to the macrocyclic ring. The most preferred compounds are those wherein the substituents R represent imidazole groups and the most preferred compound is mesotetrakis(2-imidazo1yl) porphyrin. The porphyrins having the Formula I may be prepared by syntheses known in the art. In particular, by the Rothermund synthesis in which pyrrole is added to a solution of an aldehyde having the formula RCHO wherein R represents any of the substituent groups R-j , R , R3, R4 as defined above in propionic acid.
The 1:1 metal complexes of the tetrapyrrolic macrocyclic compounds described above may also exhibit conduction properties and molecular-electronic devices comprising such complexes form a further aspect of this invention. These complexes may be prepared using processes known to be useful in the art. The nickel, palladium and platinum complexes of the porphyrins and phthalocyanines are especially useful and form a preferred aspect of this invention. The ferric iron and cupric copper complexes are also of particular value. The metal complexes may find particular application as a conducting material in molecular-electronic devices since they may exhibit both proton and electronic conduction. Devices wherein the conducting material exhibits this dual conduction capability form another aspect of this invention.
The invention is illustrated by the following examples. Example 1
Mesotetrakis(2-imidazolyl)porphyrin (TIP), was prepared via the Rothemund procedure by refluxing equimolar amounts of imidazole-2-carboxaldehyde and pyrrole in propionic acid. Analytically pure product was obtained by washing the solid precipitated from the cooled reaction mixture with chloroform, acetone and methanol .
The material could not be chromatographed on silica gel. The product was found not to be soluble in neutral aqueous solutions. However, it was soluble in solutions at pH = 2 or less.
Uv/visible spectra recorded between 400 nm and 700 n and from pH = 2 (0.01M HC1 , porphyrin free-base) to pH = -1.08 (12M HC1 , porphyrin dication) did not show a coherent set of pH- dependant isobestic points for both the B band and Q band spectra.
The IR spectrum of the product ( Br disc) shows a broad, intense absorption between 2400 cm-1 and 3600 cm-1, similar to that shown by imidazole.
Samples of TIP were therefore subjected to proton- conductivity studies, along with tetraphenyl porphyrin (TPP) which was used as a non-hydrogen bonded reference compound.
Compressed discs of TIP and TPP were prepared. These were retained between spring-loaded electrodes composed of Pt black electrochemically deposited on a copper substrate in a vacuum- tight environment, in which the partial pressure of water was closely controlled.
Initial D. C. conductivity measurement on a TIP sample under nitrogen, without prior evacuation of the test cell to remove water, gave a conductivity of 1.2*10~6 S m~- . Under the same conditions, the TPP sample gave a much lower conductivity of <3*10-14 S πH . Dehydration of the samples by evacuating the test cell, reduced the conductivity of the TIP to 1.6*10-11 S m-1, while that of the TPP remained virtually unchanged at 1*10"14 S πr1.
Another sample of TIP was evacuated overnight at 10-2 torr, to remove bound water. It was then allowed to equilibrate in the test cell with an atmosphere containing water vapour at 11.3% partial pressure. The conductivity of the TIP sample was then measured and found to be 6.8*10"12 S m~■ . A pulse of dry hydrogen gas was then admitted to the cell and the conductivity was observed to rise by nearly four orders of magnitude to 2.8*10-8 S m"1 , demonstrating that conductivity in TIP is protonic and hydration dependant.
Evidence that TIP has a stacked arrangement of monomeric subunits in the solid state has, however, been provided by powder X-ray diffraction studies. While the data obtained could not be unequivocally indexed, solutions obtained by a program were consistent with there being one short crystallographic axis. Values for the unit cell dimensions obtained in this way are:- a = 3.6±0.2A; b *■= 17.0±0.3A; c = 20.65±0.25A Example 2 The porphyrin mesotetrakis (2-imidazoyl) porphyrin (TIP) (lO gs; 0.0175mM) was warmed with stirring in dilute hydrochloric acid (0.01M; 3ml) until it dissolved. UV/visible spectroscopy of this solution showed a four banded visible spectrum demonstrating that the TIP is not protonated on its central nitrogen atoms.
A saturated aqueous solution of nickel chloride (lO ls) was then added with warming. The UV/visible spectrum showed a collapse of the four banded spectrum to a two banded spectrum after a period of about three hours. The mixture was allowed to cool to ambient temperature then several drops of 0.880 ammonia were added. The 1:1 nickel porphyrin complex precipitated out leaving the excess nickel in solution in the form of its hexammine complex.

Claims

What we claim is:
1. A molecular-electronic device wherein the conducting material comprises a macrocyclic compound which is capable of forming columnar stacks said compound containing at least one substituent capable of forming a hydrogen bond as part of its molecular structure.
2. A device according to claim 1 characterised in that hydrogen bonds are formed between adjacent macrocyclic compounds in a columnar stack.
3. A device according to claim 2 characterised in that at least three hydrogen bonds are formed between the adjacent macrocyclic compounds.
4. A device according to claim 3 characterised in that at least four hydrogen bonds are formed between the adjacent macrocyclic compounds.
5. A device according to any of the preceding claims characterised in that the macrocyclic compound is a tetrapyrrolic macrocyclic compound.
6. A device according to claim 5 characterised in that the tetrapyrrolic macrocyclic compound is a phthalocyanine.
7. A device according to claim 5 characterised in that the tetrapyrrolic macrocyclic compound is a porphyrin.
8. A device according to claim 7 characterised in that the porphyrin has the formula:
Figure imgf000008_0001
wherein at least three of the substituents R-j , R2. 3 and R4 which may be the same of different represents a group comprising at least one hydroxyl , carboxyl primary amine or secondary amine function.
9. A device according to claim 8 characterised in that the substituents R-j , R2, R3 and R4 represent a heterocyclic group comprising at least one nitrogen atom as part of the cyclic species.
10. A device according to claim 9 characterised in that the substituents are selected from the group comprising imidazole, pyrimidine and purine.
11. A device according to claim 10 characterised in that the substituent is a 2-imidazole group.
12. A device according to claim 11 characterised in that the macrocyclic compound is mesotetrakis(2-imidazoyl ) porphyrin.
13. A device according to any of the preceding claims characterised in that the mode of conduction is at least partially that of proton conductance.
14. A device according to any of the preceding claims characterised in that the macrocyclic compound is present as a
1:1 metal complex.
15. A device according to claim 14 characterised in that the metal complex is a nickel, palladium, platinum, ferric iron or cupric copper complex.
16. A device according to either of claims 10 or 11 characterised in that the macrocyclic compound is present in the form of its nickel complex.
17. A macrocyclic compound which is useful as a conducting material in a device according to any of claims 1 to 13.
18. Mesotetrakis(2-imidazoyl) porphyrin which is characterised in that it exhibits proton conductance in the solid state.
19. A process for the preparation of a macrocyclic compound useful in a device according to claim 8 which comprises reacting pyrrole with an aldehyde having the formula RCH0 wherein R represents any or all of the substituents R-, , R2, R3 and R4.
20. A device according to any of the preceding claims substantially as hereinbefore described with reference to the foregoing examples.
PCT/GB1992/000338 1991-02-26 1992-02-25 Molecular-electronic devices WO1992015099A1 (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493017A (en) * 1992-08-14 1996-02-20 The Trustees Of The University Of Pennsylvania Ring-metalated porphyrins
US5756723A (en) * 1992-08-14 1998-05-26 The Trustees Of The University Of Pennsylvania Metal-mediated cross-coupling with ring-metalated porphyrins
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
US5856515A (en) * 1992-08-14 1999-01-05 Trustees Of The University Of Pennsylvania Electron-deficient porphyrins and processes and intermediates for preparing same
US6479477B1 (en) 1998-04-24 2002-11-12 Duke University Substituted porphyrins
US6583132B1 (en) 1993-10-15 2003-06-24 Duke University Oxidant scavengers
US6916799B2 (en) 1997-11-03 2005-07-12 Duke University Substituted porphyrins
US7485721B2 (en) 2002-06-07 2009-02-03 Duke University Substituted porphyrins
US7820644B2 (en) 1999-01-25 2010-10-26 Aelous Pharmaceuticals, Inc. Substituted porphyrins
US8470808B2 (en) 1999-01-25 2013-06-25 Jon D. Piganelli Oxidant scavengers for treatment of type I diabetes or type II diabetes
CN103232459A (en) * 2013-04-26 2013-08-07 广西大学 Synthesis method of semi-cucurbit[4]uril taking propyleneurea as unit
US11382895B2 (en) 2008-05-23 2022-07-12 National Jewish Health Methods for treating injury associated with exposure to an alkylating species

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002241633A1 (en) * 2000-10-30 2002-06-11 The Trustees Of Columbia University In The City Of New York Self-assembled nanostructures with macroscopic polar order
US20050065304A1 (en) * 2001-05-30 2005-03-24 Masumi Asakawa Monomer having rotaxane structure and polymers and processes for production of both

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US2951799A (en) * 1957-11-13 1960-09-06 Monsanto Chemicals Photoxidation processes using heterocyclic photosensitizers
US4304719A (en) * 1981-01-23 1981-12-08 The United States Of America As Represented By The Secretary Of The Navy Conducting iodine-doped fluorometallophthalocyanines
EP0134171A1 (en) * 1983-08-03 1985-03-13 Societe Nationale Elf Aquitaine Oxygen sensor with a work electrode composed of a macrocyclic pyrolic compound
US4563301A (en) * 1982-12-13 1986-01-07 Northwestern University Electrically conductive low dimensional organomacrocycle compositions, articles and fabrication methods
DE4001158A1 (en) * 1990-01-17 1991-07-18 Basf Ag Macrocyclic polymer contg. phthalocyanine or porphyrin gps. - with high heat and dimensional stability, hardness and heat conductivity

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US5104637A (en) * 1985-02-06 1992-04-14 University Of Cincinnati Radio labeled dihematophorphyrin ether and its use in detecting and treating neoplastic tissue

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951799A (en) * 1957-11-13 1960-09-06 Monsanto Chemicals Photoxidation processes using heterocyclic photosensitizers
US4304719A (en) * 1981-01-23 1981-12-08 The United States Of America As Represented By The Secretary Of The Navy Conducting iodine-doped fluorometallophthalocyanines
US4563301A (en) * 1982-12-13 1986-01-07 Northwestern University Electrically conductive low dimensional organomacrocycle compositions, articles and fabrication methods
EP0134171A1 (en) * 1983-08-03 1985-03-13 Societe Nationale Elf Aquitaine Oxygen sensor with a work electrode composed of a macrocyclic pyrolic compound
DE4001158A1 (en) * 1990-01-17 1991-07-18 Basf Ag Macrocyclic polymer contg. phthalocyanine or porphyrin gps. - with high heat and dimensional stability, hardness and heat conductivity

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493017A (en) * 1992-08-14 1996-02-20 The Trustees Of The University Of Pennsylvania Ring-metalated porphyrins
US5756723A (en) * 1992-08-14 1998-05-26 The Trustees Of The University Of Pennsylvania Metal-mediated cross-coupling with ring-metalated porphyrins
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
US5856515A (en) * 1992-08-14 1999-01-05 Trustees Of The University Of Pennsylvania Electron-deficient porphyrins and processes and intermediates for preparing same
US6583132B1 (en) 1993-10-15 2003-06-24 Duke University Oxidant scavengers
US6916799B2 (en) 1997-11-03 2005-07-12 Duke University Substituted porphyrins
US6479477B1 (en) 1998-04-24 2002-11-12 Duke University Substituted porphyrins
US7820644B2 (en) 1999-01-25 2010-10-26 Aelous Pharmaceuticals, Inc. Substituted porphyrins
US8217026B2 (en) 1999-01-25 2012-07-10 Aeolus Sciences, Inc. Substituted porphyrins
US8470808B2 (en) 1999-01-25 2013-06-25 Jon D. Piganelli Oxidant scavengers for treatment of type I diabetes or type II diabetes
US8546562B2 (en) 1999-01-25 2013-10-01 James D. Crapo Substituted porphyrins
US8946202B2 (en) 1999-01-25 2015-02-03 Aeolus Sciences, Inc. Substituted porphyrins
US9289434B2 (en) 1999-01-25 2016-03-22 Aeolus Sciences, Inc. Substituted porphyrins
US7485721B2 (en) 2002-06-07 2009-02-03 Duke University Substituted porphyrins
US11382895B2 (en) 2008-05-23 2022-07-12 National Jewish Health Methods for treating injury associated with exposure to an alkylating species
CN103232459A (en) * 2013-04-26 2013-08-07 广西大学 Synthesis method of semi-cucurbit[4]uril taking propyleneurea as unit

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GB9103991D0 (en) 1991-04-10
GB9204028D0 (en) 1992-04-08
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JPH06503204A (en) 1994-04-07
GB2253209A (en) 1992-09-02

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