Quinoid compounds and their use in semiconducting matrix materials, electronic and optoelectronic structural elements

Abstract

The invention relates to quinoid compounds and their use in semiconductive matrix materials, electronic and optoelectronic structural elements.

Claims

1. A quinoid compound or derivative thereof, wherein the quinoid compound is selected from the group consisting of: ##STR00010## ##STR00011## wherein: R.sup.1-R.sup.8 are independently selected from halogen, CN, NO.sub.2, COR, perhalogenated or partially halogenated C.sub.1-C.sub.10 alkyl groups, substituted or unsubstituted electron-withdrawing aryl-, or substituted or unsubstituted electron-withdrawing heteroaryl groups; R.sup.10-R.sup.15 are independently selected from hydrogen, halogen, CN, NO.sub.2, COR, C.sub.1-C.sub.10 alkyl, perfluorinated C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, substituted or unsubstituted electron-withdrawing aryl-, or substituted or unsubstituted electron-withdrawing heteroaryl groups; X, X.sub.1, Y, and Y.sub.1 are independently selected from: ##STR00012## wherein: Z is selected from halogen, NO.sub.2, NO, CF.sub.3, COR, or SO.sub.2R; R is selected from substituted or unsubstituted C.sub.1-C.sub.10 alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Ar is an acceptor-substituted and halogenated aromatic hydrocarbon; and Hetaryl is an acceptor-substituted and/or halogenated, electron-withdrawing aromatic heterocyclic compound.

2. The quinoid compounds according to claim 1, wherein R.sup.1-R.sup.8 are selected independently from fluorine or perfluorinated C.sub.1-C.sub.10 alkyl groups.

3. The quinoid compounds according to claim 1, wherein R.sup.10-R.sup.15 are selected independently from perfluorinated C.sub.1-C.sub.10 alkyl groups.

4. The quinoid compounds according to claim 1, wherein the acceptor substituent of Ar is a nitrile group, and the other positions of Ar are halogenated with fluorine atoms.

5. The quinoid compounds according to claim 1, wherein Ar is a polycyclic compound or biaryl.

6. The quinoid compounds according to claim 1, wherein the acceptor-substituent of Hetaryl is a nitrile group.

7. The quinoid compounds according to claim 1, wherein Hetaryl is a polycyclic compound.

8. The quinoid compounds according to claim 1, wherein Hetaryl is completely halogenated by fluorine.

9. An electronic or optoelectronic structural element comprising a dopant for doping an organic semiconductive matrix material, a charge injection layer, a hole blocker layer, an electrode material, a transport material, or a storage material, wherein the dopant for doping an organic semiconductive matrix material, the charge injection layer, the hole blocker layer, the electrode material, the transport material, or the storage material comprises a quinoid compound or derivative thereof, wherein the quinoid compound is selected from the group consisting of: ##STR00013## ##STR00014## wherein: R.sup.1-R.sup.8 are independently selected from halogen, CN, NO.sub.2, COR, perhalogenated or partially halogenated C.sub.1-C.sub.10 alkyl groups, substituted or unsubstituted electron-withdrawing aryl-, or substituted or unsubstituted electron-withdrawing heteroaryl groups; R.sup.10-R.sup.15 are independently selected from hydrogen, halogen, CN, NO.sub.2, COR, C.sub.1-C.sub.10 alkyl, perfluorinated C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, substituted or unsubstituted electron-withdrawing aryl-, or substituted or unsubstituted electron-withdrawing heteroaryl groups; X, X.sub.1, Y, and Y.sub.1 are independently selected from: ##STR00015## wherein: Z is selected from halogen, NO.sub.2, NO, CF.sub.3, COR, or SO.sub.2R; R is selected from substituted or unsubstituted C.sub.1-C.sub.10 alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Ar is an acceptor-substituted and halogenated aromatic hydrocarbon; and Hetaryl is an acceptor-substituted and/or halogenated, electron-withdrawing aromatic heterocyclic compound.

10. The electronic or optoelectronic structural element of claim 9, comprising the organic semiconductive matrix material and the dopant, wherein the dopant comprises at least one of the quinoid compounds or derivatives thereof.

11. The electronic or optoelectronic structural element according to claim 10, wherein the molar doping ratio of dopant to matrix molecule or the doping ratio of dopant to monomeric units of a polymeric matrix molecule is between 20:1 and 1:100000.

12. The electronic or optoelectronic structural element according to claim 9, comprising an electronically functionally active area, wherein the electronically active area comprises at least one of the quinoid compounds or derivatives thereof.

13. The electronic or optoelectronic structural element according to claim 12, wherein the electronically active area comprises the organic semiconductive matrix material doped with at least one of the dopant, wherein the dopant changes the electronic properties of the organic semiconductive matrix material, wherein the dopant comprises at least one of the quinoid compounds or derivatives thereof.

14. The electronic or optoelectronic structural element according to claim 12, wherein the element is an organic light-emitting diode, a photovoltaic cell, an organic solar cell, an organic diode, or an organic field effect transistor.

Description

EXAMPLES OF SYNTHESIS

Dihydro Compounds

Synthesis of 4,4-Decafluorodibenzhydryenl-2,3,5,6,2,3,5,6-octafluorobiphenylene

(1) ##STR00007##

(2) 2 eq dipentafluorophenyl-t-butylmethane in a little glyme are slowly compounded under ice cooling and protective gas to a suspension of 2 eq sodium hydride in glyme. After the addition has been concluded the mixture is agitated 30 min longer at room temperature. 1 eq decafluorobiphenyl is rapidly added and the mixture heated 3 h at 60 C. After cooling off, the mixture is precipitated with water and washed with a little methanol and ether. The obtained product is converted in an atmosphere of protective gas for a few minutes in boiling diphenylether under splitting off of butane into the yellow-orangish product, which can be removed by suction after cooling off. Fp.: >250 C.

Synthesis of 3,6 bis[1-cyano-1-(4-cyano-tetrafluorophenyl)-methylene]-2,5-difluoro-phenyl-1,4-dicarbonitrile

(3) ##STR00008##

(4) 2.5 mmol tetrafluoroterephthalonitrile and 5.1 mmol NaH were suspended in 50 ml dimethoxyethylene under argon. 6.0 mmol (1.28 g) 2-t-butyl-4-cyanotetrafluorophenylacetonitrile in 5 ml dimethoxyethylene were dropped at 5 C. into this mixture. After 30 h agitation at room temperature the mixture was poured onto 200 ml ice water and acidified with hydrochloric acid. The purple-colored solid obtained was filtered off and dried in the vacuum. The product was purified by recrystallization from a suitable solvent and butane subsequently split off in diphenylether at 250 C. After cooling off, ether was added and the mixture adjusted cold. The precipitated product was removed by suction and dried in the vacuum. (yield 1.55 g). ESE-MS analysis (negative detection, direct inlet from a solution in MeOH/0.5 mM NH4OAc): m/z=587 [M-H].sup., 293 [M2H].sup.2.

Synthesis of the Quinoid Compounds (Oxidation)

Synthesis von 3,6-bis[1-cyano-1-(4-cyano-phenyl)-methylidene]-2,5-difluoro-cyclohexa-1,4-diene-1,4-dicarbonitrile

(5) ##STR00009##

(6) The corresponding dihydro compound was compounded without further purification to the complete solution with glacial acetic acid and a mixture of nitric acid and hydrobromic acid cooled to 0 C. added. After the conclusion of the addition the mixture was agitated still at room temperature, compounded with water until the start of the precipitation of a solid and agitated further at room temperature. The orange-colored solid was removed by suction, washed with water and dried in the vacuum (yield over all stages 76%). DI-MS (EI): m/z=586 [M].sup.+. .sup.19F-NMR (CD.sub.3CN): =100.5 (m, 2F), 127.7 (m, 4F), 131.6 (m, 4F) ppm.

APPLICATION EXAMPLES FOR THE DOPING

(7) An extremely electron-poor and electron-withdrawing quinoid compound is provided very cleanly.

(8) The electron-poor quinoid compound placed in a receiver is evaporated simultaneously with the matrix material. According to the exemplary embodiment the matrix material is phthalocyanine zinc, spiro-TTB or a-NDP. The p-dopant and the matrix material can be evaporated in such a manner that the layer precipitated on a substrate in a vacuum evaporation system has a doping ratio of p-dopant to matrix material of 1:10.

(9) The particular layer of the organic semi-conductor material doped with the p-dopant is applied on an ITO layer (indium tin oxide) arranged on a glass substrate. After the application of the p-doped organic semiconductor layer a metal cathode is applied, for example, by vapor-depositing a suitable metal in order to produce an organic light-emitting diode. It is understood that the organic light-emitting diode can also have a so-called inverted layer construction in which the layer sequence is: glass substrate-metal cathode-p-doped organic layer-transparent conductive cover layer (for example ITO). It is understood that further layers can be provided between the individual cited layers depending on the application.

Doping with_3,6-bis[1-cyano-1-(4-cyano-phenyl)-methylidene]-2,5-difluoro-cyclohexa-1,4-diene-1,4-dicarbonitrile

(10) The doping performance was checked by Co evaporation of 3,6-bis[1-cyano-1-(4-cyano-phenyl)-methylidene]-2,5-difluoro-cyclohexa-1,4-diene-1,4-dinitrile (5 mol %) with spiro TTB and measuring the conductivity of the mixed layer obtained. A conductivity of the doped layer of 1.810.sup.4 Scm.sup.1 was found.

(11) The features of the invention disclosed in the above description and in the claims can be essential individually as well as in any combination for the realization of the invention in its different embodiments.