Substituted 1,2,3-triylidenetris(cyanomethanylylidene) cyclopropanes for VTE, electronic devices and semiconducting materials using them

Patent metadata

Field	Value
Publication number	US-10128442-B2
Application number	US-201515536778-A
Country	US
Kind code	B2
Filing date	Dec 16, 2015
Priority date	Dec 16, 2014
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

Provided are processes for preparing an electrically doped semiconducting material that includes a [3]-radialene p-dopant. Also provided are processes for preparing an electronic device containing a layer that includes a [3]-radialene p-dopant. The processes may include (i) loading an evaporation source with a [3]-radialene p-dopant and (ii) evaporating the [3]-radialene p-dopant at an elevated temperature and at a reduced pressure. The [3]-radialene p-dopant may be selected from compounds having a structure according to formula (I) herein.

First claim

The invention claimed is:

1. A process for preparation of an electrically doped semiconducting material comprising a [3]-radialene p-dopant or for preparation of an electronic device including a layer comprising a [3]-radialene p-dopant, the process comprising the steps:
(i) loading an evaporation source with the [3]-radialene p-dopant and
(ii) evaporating the [3]-radialene p-dopant at an elevated temperature and at a reduced pressure,
wherein the [3]-radialene p-dopant is selected from compounds having a structure according to formula (I)

wherein A 1 and A 2 are independently aryl- or heteroaryl-substituted cyanomethylidene groups,
the aryl and/or heteroaryl is selected independently in A 1 and A 2 from 4-cyano-2,3,5,6-tetrafluorphenyl, 2,3,5,6-tetrafluorpyridine-4-yl, 4-trifluormethyl-2,3,5,6-tetrafluorphenyl, 2,4-bis(trifluormethyl)-3,5,6-trifluorphenyl, 2,5-bis(trifluormethyl)-3,4,6-trifluorphenyl, 2,4,6-tris(trifluormethyl)-1,3-diazine-5-yl, 3,4-dicyano-2,5,6-trifluorphenyl, 2-cyano-3,5,6-trifluorpyridine-4-yl, 2-trifluormethyl-3,5,6-trifluorpyridine-4-yl, 2,5,6-trifluor-1,3-diazine-4-yl and 3-trifluormethyl-4-cyano-2,5,6-trifluorphenyl,
and at least one aryl or heteroaryl is 2,3,5,6-tetrafluorpyridine-4-yl, 2,4-bis(trifluormethyl)-3,5,6-trifluorphenyl, 2,5-bis(trifluormethyl)-3,4,6-trifluorphenyl, 2,4,6-tris(trifluormethyl)-1,3-diazine-5-yl, 3,4-dicyano-2,5,6-trifluorphenyl, 2-cyano-3,5,6-trifluorpyridine-4-yl, 2-trifluormethyl-3,5,6-trifluorpyridine-4-yl, 2,5,6-trifluor-1,3-diazine-4-yl or 3-trifluormethyl-4-cyano-2,5,6-trifluorphenyl,
provided that the heteroaryl in both A 1 and A 2 cannot be 2,3,5,6-tetrafluorpyridine-4-yl at the same time.

2. The process according to claim 1 , wherein the temperature in step (ii) is in the range 100-300° C.

3. The process according to claim 1 , wherein the duration of the step (ii) is at least 100 hours.

4. The process according to claim 1 , wherein in the step (ii), a hole transport material comprising at least one hole transport matrix compound is co-evaporated with the compound having structure (I) and, in a subsequent step (iii), the compound (I) and the hole transport matrix compound are co-deposited to form a semiconducting material.

5. The process according to claim 1 , wherein the step (ii) is carried out at a pressure which is lower than 10 −1 Pa.

6. The process according to claim 1 , wherein compound (I) has reversible redox potential, measured by cyclic voltammetry in acetonitrile against ferrocene/ferricenium reference system, in the range from +0.10 to +0.50 V.

7. A [3]-radialene compound having a structure according to formula (I):

wherein
A 1 and A 2 are independently aryl- or heteroaryl-substituted cyanomethylidene groups, the aryl and/or heteroaryl is selected independently in A 1 and A 2 from 4-cyano-2,3,5,6-tetrafluorphenyl, 2,3,5,6-tetrafluorpyridine-4-yl, 4-trifluormethyl-2,3,5,6-tetrafluorphenyl, 2,4-bis(trifluormethyl)-3,5,6-trifluorphenyl, 2,5-bis(trifluormethyl)-3,4,6-trifluorphenyl, 2,4,6-tris(trifluormethyl)-1,3-diazine-5-yl, 3,4-dicyano-2,5,6-trifluorphenyl, 2-cyano-3,5,6-trifluorpyridine-4-yl, 2-trifluormethyl-3,5,6-trifluorpyridine-4-yl, 2,5,6-trifluor-1,3-diazine-4-yl and 3-trifluormethyl-4-cyano-2,5,6-trifluorphenyl,
and at least one aryl or heteroaryl is 2,3,5,6-tetrafluorpyridine-4-yl, 2,4-bis(trifluormethyl)-3,5,6-trifluorphenyl, 2,5-bis(trifluormethyl)-3,4,6-trifluorphenyl, 2,4,6-tris(trifluormethyl)-1,3-diazine-5-yl, 3,4-dicyano-2,5,6-trifluorphenyl, 2-cyano-3,5,6-trifluorpyridine-4-yl, 2-trifluormethyl-3,5,6-trifluorpyridine-4-yl, 2,5,6-trifluor-1,3-diazine-4-yl or 3-trifluormethyl-4-cyano-2,5,6-trifluorphenyl,
provided that the heteroaryl in both A 1 and A 2 cannot be 2,3,5,6-tetrafluorpyridine-4-yl at the same time.

8. The compound according to claim 7 , having reversible redox potential, measured by cyclic voltammetry in acetonitrile against ferrocene/ferricenium reference system, in the range from +0.10 to +0.50 V.

9. A semiconducting material comprising the compound according to claim 7 and a matrix material comprising at least one hole transport matrix compound.

10. An electronic device comprising, between a first and a second electrode, the semiconducting material according to claim 9 .

11. The electronic device according to claim 10 , which is an organic light emitting diode.

12. The electronic device according to claim 10 , wherein the compound having formula (I) is comprised in a hole injecting layer and/or in a hole transporting layer and/or in a charge generating layer.

13. A semiconducting layer consisting of the semiconducting material according to claim 9 .

14. A semiconducting layer consisting of the compound according to claim 7 .

15. An electronic device comprising, between a first and a second electrode, the semiconducting layer according to claim 14 .

16. The electronic device according to claim 15 , which is an organic light emitting diode.

17. The electronic device according to claim 15 , wherein the compound having formula (I) is comprised in a hole injecting layer and/or in a hole transporting layer and/or in a charge generating layer.

18. Use of the compound according to claim 7 as a p-dopant in a semiconducting material, in a semiconducting layer, or in an electronic device.

19. A process for synthesis of the [3]-radialene compound according to claim 7 ,
wherein a last synthesis step consists of oxidizing a reduced form of the compound of formula (I) to form the compound of formula (I), and the last synthesis step is carried out in a solvent comprising at least one saturated halogenated carboxylic acid.

Assignees

• Novaled Gmbh

Inventors

• Hummert Markus
• Bruch Achim
• Köhn Christiane
• Nüllen Max P
• Heggemann Ulrich

Classifications

• C09K11/06

  containing organic luminescent materials · CPC title

• C07C255/51

  containing at least two cyano groups bound to the carbon skeleton · CPC title

• H01L51/506

  Electricity · mapped topic

• C09K2211/1007

  Non-condensed systems · CPC title

• H01L2251/554

  Electricity · mapped topic