Heteroleptic copper complexes for optoelectronic uses

Patent metadata

Field	Value
Publication number	US-9985225-B2
Application number	US-201214357805-A
Country	US
Kind code	B2
Filing date	Nov 16, 2012
Priority date	Nov 16, 2011
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

A heteroleptic binuclear copper(I) complex of the Cu 2 X 2 (E∩N*)L 2 form, having a structure of formula A:

The copper(I) complex may be used in optoelectronic components, particularly for use in organic light emitting diodes (OLEDs).

First claim

The invention claimed is:

1. A copper(I) complex comprising a structure of formula A:

wherein
each X* is independently selected from Cl, Br, I, CN, OCN, SCN, alkynyl and N 3 ;
N*∩E is a bidentate ligand, wherein
E is selected from a phosphanyl group, an arsenyl group, and an antimonyl group of the form R 2 E, wherein R is selected from alkyl, aryl, heteroaryl, alkoxyl, phenoxyl, and amide;
N* is an imine function which is part of an aromatic group selected from pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, tetrazinyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, tetrazolyl, 1,2,3,4-oxatriazolyl, 1,2,3,4-thiatriazole, chinoxalyl, and chinazolyl;
∩ is one carbon atom which is likewise part of the aromatic group, wherein the carbon atom is directly adjacent both to the imine nitrogen atom and to one of a phosphorus atom of the phosphanyl group, an arsenic atom of the arsenyl group, or an antimony atom of the antimonyl group; and

ligands L are each monodentate ligand in the form DR 3 , wherein D is selected from P, As and Sb, wherein R is each independently selected from hydrogen, halogen, alkyl, heteroalkyl, aryl, alkenyl, alkynyl groups or substituted alkyl, heteroalkyl, aryl and alkenyl groups with substituents selected from halogens and deuterium, alkyl groups, heteroalkyl, aryl, heteroaryl and donor and acceptor groups selected from amines, carboxylates and their esters and CF 3 groups, wherein the alkyl group or the substituted alkyl group is optionally bound to D via an oxygen atom and wherein the three R groups optionally lead to annulated ring systems;

or
the ligands L are connected to each other via a bridge B such that a bidentate ligand in the form R 2 D-B-DR 2 results, wherein D is selected from P, As and Sb, wherein the bridge B is a direct bond or a substituted or unsubstituted alkylene, alkenylene, alkynylene or arylene group or a combination of both, or —O—, —NR— or —SiR 2 —, wherein R is each independently selected from hydrogen, halogen, alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl, heteroalkyl, aryl, heteroaryl and alkenyl groups with substituents selected from halogens and deuterium, alkyl groups, heteroalkyl, aryl, heteroaryl and donor and acceptor groups selected from amines, carboxylates and their esters and CF 3 groups, and wherein the alkyl or the substituted alkyl is optionally bound to D via an oxygen atom and wherein the two R groups optionally lead to annulated ring systems;

wherein ligand N*∩E comprises at least one substituent selected from the group consisting of:
branched, unbranched or cyclic alkyl chains with a length of C1 to C30;
branched, unbranched or cyclic alkoxy chains with a length of C1 to C30;
branched, unbranched or cyclic perfluoroalkyl chains with a length of C1 to C30; and
polyethers with a chain length of 5-50 repeat units.

2. The copper(I) complex of claim 1 , wherein the ligand N*∩E is selected from the group consisting of

wherein
E* is selected from P, As and Sb;
X is selected from NR 3 , O and S;
Y is selected from CR 3 and N;
Z is selected from CR 4 and N;
R 1 , R 2 are each independently selected from alkyl, aryl, heteroaryl, alkoxyl, phenoxyl, and amide;
R 3 -R 5 are each independently selected from hydrogen, halogen, alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl, heteroalkyl, aryl, heteroaryl and alkenyl groups with substituents selected from halogens and deuterium, alkyl groups, heteroalkyl, aryl, heteroaryl and donor and acceptor groups selected from amines, carboxylates and their esters and CF 3 groups; R 3 -R 5 optionally lead to annulated ring systems;
wherein the ligand N*∩E comprises at least one of R 1 -R 5 that comprises:
a branched, unbranched or cyclic alkyl chain with a length of C1 to C30;
a branched, unbranched or cyclic alkoxy chain with a length of C1 to C30;
a branched, unbranched or cyclic perfluoroalkyl chain with a length of C1 to C30; and
a polyether with a chain length of 5-50 repeat units;

wherein each D of the monodentate ligands in the form DR 3 or each D of the bidentate ligand R 2 D-B-DR 2 is P;
wherein R of the monodentate ligands in the form DR 3 or R of the bidentate ligand R 2 D-B-DR 2 is selected from hydrogen, halogen, alkyl, heteroalkyl, aryl, alkenyl, alkynyl groups or substituted alkyl, heteroalkyl, aryl and alkenyl groups with substituents selected from halogens or deuterium, alkyl groups, heteroalkyl, aryl, heteroaryl and further donor and acceptor groups selected from amines, carboxylates and their esters and CF 3 groups; wherein the alkyl or the substituted alkyl is optionally bound to D via an oxygen atom; the individual R groups optionally lead to annulated ring systems; and
wherein R 2 D-B-DR 2 is selected from:

3. The copper(I) complex of claim 1 , wherein at least one of the ligand N*∩E and the ligands L comprise at least one substituent selected from the group consisting of an electron conductor and a hole conductor.

4. The copper(I) complex of claim 1 , wherein each X* is independently selected from Cl, Br, and I.

5. A method for the production of the copper(I) complex of claim 4 , comprising conducting a reaction of the ligand N*∩E and the ligand L with Cu(I)X, wherein X is selected from Cl, Br, and I.

6. The method of claim 5 , wherein the reaction is conducted in at least one of dichloromethane, acetonitrile, tetrahydrofuran, dimethylsulfoxide and ethanol.

7. The method of claim 6 , further comprising the step of adding at least one of diethyl ether, pentane, hexane, methyl-tert-butyl ether, methanol, ethanol and water for obtaining the copper(I) complex in the form of a solid.

8. The method of claim 5 , wherein the copper(I) complex is soluble in an organic solvent,
wherein the organic solvent is selected from the group consisting of alcohols, ethers, alkanes, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, and alkylated aromatic hydrocarbons.

9. The method of claim 5 , further comprising the step of substituting at least one of the ligand N*∩E and the ligand L with at least one functional group for improving a charge carrier transport selected from an electron conductor and a hole conductor.

10. An optoelectronic component comprising at least one of:
an emitter comprising the copper(I) complex of claim 1 ; and
an absorber comprising the copper(I) complex of claim 1 .

11. The optoelectronic component of claim 10 , wherein the optoelectronic component is one of:
an organic light emitting diode (OLED);
a light emitting electrochemical cell;
a OLED sensor;
an organic solar cell;
an organic field-effect transistor;
an organic laser; and
a down-conversion element.

12. An optoelectronic device comprising the copper(I) complex of claim 1 , wherein the optoelectronic device is in the form of a component selected from the group consisting of an organic light emitting component, an organic diode, an organic solar cell, an organic transistor, an organic light emitting diode, a light emitting electrochemical cell, an organic field-effect transistor and an organic laser.

13. A method for the product

Assignees

• Cynora Gmbh

Inventors

• Baumann Thomas
• Grab Tobias
• Volz Daniel
• Zink Daniel

Classifications

• C09K2211/1048

  with oxygen · CPC title

• C09K2211/1059

  containing three nitrogen atoms as heteroatoms · CPC title

• C09K2211/1051

  with sulfur · CPC title

• C09K11/06

  containing organic luminescent materials · CPC title

• C07F9/65312

  having the two nitrogen atoms in positions 1 and 2 · CPC title