PT- OR PD-CARBENE COMPLEXES FOR USE IN ORGANIC LIGHT EMITTING DIODES

Abstract

The present invention relates to Pt- or Pd-amidine-carbene complexes, to organic light-emitting diodes (OLEDs) comprising at least one such Pt- or Pd-amidine-carbene complex, to light-emitting layers comprising at least one such Pt- or Pd-amidine-carbene complex, a device, for example stationary or mobile visual display units or illumination means, comprising a corresponding OLED, and to the use of the inventive Pt- or Pd-amidine-carbene complexes in OLEDs, for example as emitters, matrix materials, charge transport materials and/or charge blockers.

Claims

1. A complex of the general formula (I) or (II) ##STR00149## wherein M, A.sup.1, A.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.10 are each defined as follows: M is Pt or Pd, A.sup.1 is N or CR.sup.8, A.sup.2 is N or CR.sup.9, R.sup.1 and R.sup.2 are independently of each other a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a C.sub.1-C.sub.18haloalkyl group; or CN; R.sup.3 is hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —O—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; or CN; or R.sup.1 and R.sup.3 or R.sup.2 and R.sup.3 together form a group of formula ##STR00150## wherein X′ is present in the position of R.sup.3 and is selected from O, S, NR.sup.75 and CR.sup.73R.sup.74; R.sup.f, R.sup.g, R.sup.h, R.sup.i, R.sup.j and R.sup.k are independently of each other H, a C.sub.1-C.sub.5alkyl group, a fluoroC.sub.1-C.sub.4alkyl group, or a C.sub.3-C.sub.6cycloalkyl group; n is 0 or 1; wherein the group of formula (III) comprises 0, 1 or 2 double bonds; in the case that 1 or 2 double bonds are present in the group of formula (III), the carbon atoms connected with the double bonds are each substituted by only one residue R.sup.f, R.sup.j and/or—in the case that n is 1—R.sup.h; R.sup.5 and R.sup.6 are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —NR.sup.65—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; CN; or SiR.sup.80R.sup.81R.sup.82; or R.sup.5 and R.sup.6 together form a group of formula ##STR00151## wherein X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; R.sup.4 and R.sup.7 are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65 a halogen atom; a C.sub.1-C.sub.18haloalkyl group; CN; or SiR.sup.80R.sup.81R.sup.82; or R.sup.6 and R.sup.7 together form a group of formula ##STR00152## wherein X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; R.sup.8 and R.sup.9 are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —O—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; or CN; or R.sup.8 and R.sup.9 together form a group of formula ##STR00153## wherein Y is N or CR.sup.n; Z is N or CR.sup.o; R.sup.l, R.sup.m, R.sup.n and R.sup.o are independently of each other H, a C.sub.1-C.sub.5alkyl group, a fluoroC.sub.1-C.sub.4alkyl group, or a C.sub.3-C.sub.6cycloalkyl group; R.sup.10 is a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.65—, —SiR.sup.70R.sup.71—, —POR.sup.72—, —CR.sup.63═CR.sup.64—, or —C≡C; E is —OR.sup.69, —SR.sup.69, —NR.sup.65R.sup.66, —COR.sup.68, —COOR.sup.67, —CONR.sup.65R.sup.66, —CN, halogen, or a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; G is E; or an unsubstituted C.sub.6-C.sub.14aryl group; a C.sub.6-C.sub.14aryl group, which is substituted by F, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl, which is substituted by F and/or interrupted by O; an unsubstituted heteroaryl group comprising 5 to 11 ring atoms, interrupted by at least one of O, S, N and NR.sup.65; or a heteroaryl group comprising 5 to 11 ring atoms, interrupted by at least one of O, S, N and NR.sup.65, which is substituted by F, unsubstituted C.sub.1-C.sub.18alkyl, SiR.sup.80R.sup.81R.sup.82, or C.sub.1-C.sub.18alkyl which is substituted by F and/or interrupted by O; R.sup.63 and R.sup.64 are independently of each other H; unsubstituted C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; unsubstituted C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.65 and R.sup.66 are independently of each other H, an unsubstituted C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; or R.sup.65 and R.sup.66 together form a five or six membered ring; R.sup.67 is H, an unsubstituted C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.68 is H; an unsubstituted C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.69 is H, an unsubstituted C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.70 and R.sup.71 are independently of each other an unsubstituted C.sub.1-C.sub.18alkyl group; an unsubstituted C.sub.6-C.sub.18aryl group; or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; R.sup.72 is an unsubstituted C.sub.1-C.sub.18alkyl group; an unsubstituted C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; R.sup.73 and R.sup.74 are independently of each other H; unsubstituted C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; unsubstituted C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O; R.sup.75 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.80, R.sup.81 and R.sup.82 are independently of each other a C.sub.1-C.sub.25alkyl group, which can optionally be interrupted by O; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by C.sub.1-C.sub.18alkyl; or a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by C.sub.1-C.sub.18alkyl.

2. The complex according to claim 1, wherein M, A.sup.1 and A.sup.2, are each defined as follows: M is Pt; A.sup.1 is CR.sup.8; A.sup.2 is CR.sup.9.

3. The complex according to claim 1, wherein: R.sup.8 and R.sup.9 are independently of each other hydrogen; a C.sub.1-C.sub.12alkyl group, which can optionally be substituted by E and/or interrupted by D; or a phenyl group, which can optionally be substituted by at least one substituent G; or R.sup.8 and R.sup.9 together form a group of formula ##STR00154## wherein Y is N or CR.sup.n; Z is N or CR.sup.o; R.sup.l, R.sup.m, R.sup.n and R.sup.o are independently of each other H, a C.sub.1-C.sub.5alkyl group, C.sub.3-C.sub.6cycloalkyl group; or.

4. The complex according to claim 1, wherein: R.sup.1 and R.sup.2 are independently of each other a C.sub.1-C.sub.12alkyl group, which can optionally be substituted by at least one substituent E; a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by one or two substituents G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by one or two substituents G, interrupted by at least one of O, S, N and NR.sup.65; a C.sub.1-C.sub.18haloalkyl group; or CN; R.sup.3 is hydrogen; a C.sub.1-C.sub.12alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by one or two substituents G; a —O—C.sub.6-C.sub.14aryl group, which can optionally be substituted by one or two substituents G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by one or two substituents G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; or CN; or R.sup.1 and R.sup.3 or R.sup.2 and R.sup.3 together form a group of formula ##STR00155## wherein X′ is present in the position of R.sup.3 and is selected from O and S; n is 0 or 1; R.sup.f, R.sup.g, R.sup.h, R.sup.i, R.sup.j and R.sup.k are independently of each other H, a C.sub.1-C.sub.5alkyl group, C.sub.3-C.sub.6cycloalkyl group; wherein the group of formula (III) comprises 0 or 1 double bonds.

5. The complex according to claim 1, wherein R.sup.5 and R.sup.6 are independently of each other hydrogen; a C.sub.1-C.sub.12alkyl group, which can optionally be substituted by E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by E; a C.sub.6-C.sub.10aryl group, which can optionally be substituted by at least one substituent G; or R.sup.5 and R.sup.6 together form a group of formula ##STR00156## wherein X is O or S; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; R.sup.4 and R.sup.7 are independently of each other hydrogen; or a C.sub.1-C.sub.12alkyl group, which can optionally be substituted by E and/or interrupted by D, preferably a CH.sub.2—C.sub.1-C.sub.7alkyl group, which can optionally be substituted by E and/or interrupted by D; or R.sup.6 and R.sup.7 together form a group of formula ##STR00157## wherein X is O or S; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2.

6. The complex according to claim 1, wherein R.sup.10 is a C.sub.1-C.sub.12alkyl group, which can optionally be substituted by E; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by E; or a group of formula ##STR00158## wherein R.sup.a and R.sup.e are independently of each other hydrogen H, a C.sub.1-C.sub.5alkyl group, a fluoroC.sub.1-C.sub.4alkyl group, or a C.sub.3-C.sub.6cycloalkyl group; R.sup.c, R.sup.b and R.sup.d are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by G; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by G; or a heteroaryl group comprising 3 to 30 ring atoms, which can optionally be substituted by G; C.sub.1-C.sub.8haloalkyl; or SiR.sup.80R.sup.81R.sup.82; or R.sup.c and R.sup.b, or R.sup.a and R.sup.b together form a group of formula ##STR00159## wherein X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2.

7. The complex according to claim 1, wherein D is —O—, —S— or —NR.sup.65—; E is C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, CN, halogen, or C.sub.1-C.sub.8haloalkyl; G is a C.sub.1-C.sub.8alkyl group, or a group of formula ##STR00160## R.sup.a and R.sup.e are independently of each other H, a C.sub.1-C.sub.5alkyl group, a fluoroC.sub.1-C.sub.4alkyl group, or a C.sub.3-C.sub.6cycloalkyl group; R.sup.c, R.sup.b and R.sup.d are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by G; a heterocycloalkyl radical comprising 3 to 10 ring atoms which is interrupted by at least one of O, S and NR.sup.65 and/or substituted by E; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G; or a heteroaryl group comprising 3 to 30 ring atoms, which is interrupted by at least one of O, S and NR.sup.65 and which can optionally be substituted by G; a halogen atom; C.sub.1-C.sub.8haloalkyl; CN; or SiR.sup.80R.sup.81R.sup.82; or R.sup.c and R.sup.b, or R.sup.a and R.sup.b together form a group of formula ##STR00161## wherein X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; R.sup.65 is a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.69 is a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.73 and R.sup.74 are independently of each other a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.75 is a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.80, R.sup.81 and R.sup.82 are independently of each other a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—.

8. The complex according to claim 1, selected from structures (Ia) and (IIa): ##STR00162## wherein M is Pt or Pd, R.sup.1 and R.sup.2 are independently of each other a C.sub.1-C.sub.5alkyl group; a phenyl group, which can optionally be substituted by one or two substituents G; a heteroaryl group comprising 5 to 6 ring atoms, which can optionally be substituted by one or two substituents G, interrupted by at least one of O, S, N and NR.sup.65; or CN; R.sup.6 is hydrogen; a C.sub.1-C.sub.5alkyl group, which can optionally be substituted by at least one substituent E; a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or either R.sup.5 or R.sup.6 is a phenyl group, which can optionally be substituted by one or two groups G; R.sup.7 is hydrogen; or a C.sub.1-C.sub.5alkyl group, which can optionally be substituted by E and/or interrupted by D, or R.sup.6 and R.sup.7 together form a group of formula ##STR00163## wherein X is O or S. R.sup.8 and R.sup.9 are hydrogen; methyl; ethyl; an unsubstituted phenyl group; or a phenyl group, which is substituted by one or two C.sub.1-C.sub.8alkyl groups; or R.sup.8 and R.sup.9 together form a group of formula ##STR00164## wherein Y is N or CR.sup.n; Z is N or CR.sup.o; R.sup.l, R.sup.m, R.sup.n and R.sup.o are independently of each other H, or a C.sub.1-C.sub.5alkyl group; R.sup.10 is a C.sub.1-C.sub.5alkyl group, which can optionally be substituted by E; a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by E; or a group of formula R ##STR00165## wherein R.sup.a and R.sup.e are independently of each other H, a C.sub.1-C.sub.5alkyl group, C.sub.3-C.sub.6cycloalkyl group; R.sup.c, R.sup.b and R.sup.d are independently of each other H, a C.sub.1-C.sub.5alkyl group, C.sub.3-C.sub.6cycloalkyl group; or R.sup.c and R.sup.b, or R.sup.a and R.sup.b together form a group of formula ##STR00166## wherein X is O or S; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; D is —S— or —O—; E is —OR.sup.69, CF.sub.3, C.sub.1-C.sub.8alkyl or F; G is —OR.sup.69, CF.sub.3 or C.sub.1-C.sub.5alkyl; R.sup.65 is a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.69 is a phenyl group, which can optionally be substituted by one or two C.sub.1-C.sub.8alkyl groups; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—.

9. The complex according to claim 8, selected from the following structures: (Iaa), (Iab), (Iac), (Iad), (Iae), (Iaf), (Iag), (Iah), (Iai), (Iaj), (IIaa), (IIab), (IIac), (IIad), (IIae), (IIaf), (IIag), (IIah), (IIai) and (IIaj); wherein M is Pt or Pd: ##STR00167## ##STR00168## ##STR00169##

10. A process for preparing a complex according to claim 1, comprising the steps (i) contacting an imidazolium salt of formula (IV) ##STR00170## wherein A.sup.1 is N or CR.sup.8, A.sup.2 is N or CR.sup.9, R.sup.5 and R.sup.6 are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —NR.sup.65—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; CN; or SiR.sup.80R.sup.81R.sup.82; or R.sup.5 and R.sup.6 together form a group of formula ##STR00171## wherein X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; R.sup.4 and R.sup.7 are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65 a halogen atom; a C.sub.1-C.sub.18haloalkyl group; CN; or SiR.sup.80R.sup.81R.sup.82; or R.sup.6 and R.sup.7 together form a group of formula ##STR00172## wherein X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl and a is 0, 1 or 2; R.sup.8 and R.sup.9 are independently of each other hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —O—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; or CN; or R.sup.8 and R.sup.9 together form a group of formula ##STR00173## wherein Y is N or CR.sup.n; Z is N or CR.sup.o; R.sup.l, R.sup.m, R.sup.n and R.sup.o are independently of each other H, a C.sub.1-C.sub.5alkyl group, a fluoroC.sub.1-C.sub.4alkyl group, or a C.sub.3-C.sub.6cycloalkyl group; R.sup.10 is a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.65—, —SiR.sup.70R.sup.71—, —POR.sup.72—, —CR.sup.63═CR.sup.64—, or —C≡C; E is —OR.sup.69, —SR.sup.69, —NR.sup.65R.sup.66, —COR.sup.68, —COOR.sup.67, —CONR.sup.65R.sup.66, —CN, halogen, or a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; G is E; or an unsubstituted C.sub.6-C.sub.14aryl group; a C.sub.6-C.sub.14aryl group, which is substituted by F, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl, which is substituted by F and/or interrupted by O; an unsubstituted heteroaryl group comprising 5 to 11 ring atoms, interrupted by at least one of O, S, N and NR.sup.65; or a heteroaryl group comprising 5 to 11 ring atoms, interrupted by at least one of O, S, N and NR.sup.65, which is substituted by F, unsubstituted C.sub.1-C.sub.18alkyl, SiR.sup.80R.sup.81R.sup.82, or C.sub.1-C.sub.18alkyl which is substituted by F and/or interrupted by O; R.sup.63 and R.sup.64 are independently of each other H; unsubstituted C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; unsubstituted C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.65 and R.sup.66 are independently of each other H, an unsubstituted C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; or R.sup.65 and R.sup.66 together form a five or six membered ring; R.sup.67 is H, an unsubstituted C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.68 is H; an unsubstituted C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.17alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.69 is H, an unsubstituted C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; an unsubstituted C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.70 and R.sup.71 are independently of each other an unsubstituted C.sub.1-C.sub.18alkyl group; an unsubstituted C.sub.6-C.sub.18aryl group; or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; R.sup.72 is an unsubstituted C.sub.1-C.sub.18alkyl group; an unsubstituted C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; R.sup.73 and R.sup.74 are independently of each other H; unsubstituted C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; unsubstituted C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.75 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.80, R.sup.81 and R.sup.82 are independently of each other a C.sub.1-C.sub.25alkyl group, which can optionally be interrupted by O; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by C.sub.1-C.sub.18alkyl; or a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by C.sub.1-C.sub.18alkyl; and X.sup.− is halide, BF.sub.4.sup.−, PF.sub.6.sup.−, SbF.sub.6.sup.−, ClO.sub.4.sup.−, with a Pt salt or a Pd salt, and mixtures thereof, in the presence of a Ag or Cu(I) salt; (ii) contacting the product obtained in step (i) with a compound of formula (VII) ##STR00174## wherein R.sup.1 and R.sup.2 are independently of each other a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a C.sub.1-C.sub.18haloalkyl group; or CN; R.sup.3 is hydrogen; a C.sub.1-C.sub.18alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by at least one substituent E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one of O, S and NR.sup.65 and/or substituted by at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —O—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a heteroaryl group comprising 5 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S, N and NR.sup.65; a halogen atom; a C.sub.1-C.sub.18haloalkyl group; or CN; or R.sup.1 and R.sup.3 or R.sup.2 and R.sup.3 together form a group of formula ##STR00175## wherein X′ is present in the position of R.sup.3 and is selected from O, S, NR.sup.75 and CR.sup.73R.sup.74; R.sup.f, R.sup.g, R.sup.h, R.sup.i, R.sup.j and R.sup.k are independently of each other H, a C.sub.1-C.sub.5alkyl group, a fluoroC.sub.1-C.sub.4alkyl group, or a C.sub.3-C.sub.6cycloalkyl group; n is 0 or 1; wherein the group of formula (III) comprises 0, 1 or 2 double bonds; in the case that 1 or 2 double bonds are present in the group of formula (III), the carbon atoms connected with the double bonds are each substituted by only one residue R.sup.f, R.sup.j and/or—in the case that n is 1—R.sup.h; in the presence of a base.

11. An organic light emitting diode comprising a complex of formula (I) or (II) according to claim 1.

12. A light-emitting layer comprising a complex of formula (I) or (II) according to claim 1.

13. A light emitting layer according to claim 12 comprising the complex of formula (I) or (II) as emitter material together with at least one host material.

14. An organic light emitting diode comprising a light emitting layer according to claim 12.

15. A device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances, advertising panels, illuminations, information panels; mobile visual display units such as visual display units in smartphones, tablet computers, cellphones, laptops, digital cameras, MP3 players, vehicles and destination displays on and in buses and trains: illumination units; keyboards; items of clothing; furniture; and wallpaper, comprising the organic light emitting device according to claim 11.

16. An emitter material comprising the complex of formula (I) or (II) according to claim 1.

Description

EXAMPLES

[0509] All experiments are carried out in protective gas atmosphere. The percentages and ratios mentioned in the examples below—unless stated otherwise—are % by weight and weight ratios.

I. Synthesis Examples

[0510] I Carbene precursor synthesis

[0511] The synthesis of suitable carbene ligand precursors is well documented in literature. Procedures can be found e.g. in Enders et al. (Helvetica Chimica Acta 1996, 79, 61-83), Bielawski et al. (Inorg. Chem. 2009, 48, 6924-6933), U.S. provisional application 61/496,646, and WO2005019373.

II Complex Synthesis

II.1 Synthesis of Complex (Iaa)

[0512] A mixture of 1-(dibenzo[b,d]-3-methyl-1H-imidazolium iodide (301 mg, 0.8 mmol) and silver(I) oxide (94 mg, 0.4 mmol) in dry DMF (20 mL) is stirred under argon in the dark at 50° C. for 3 h. Dichloro(1,5-cyclooctadiene)platinum(II) (299 mg, 0.8 mmol) is added at RT and the mixture is stirred at RT for 17 h and then at 130° C. for another 24 h. After cooling to RT, N,N-diphenylformamidine (661 mg, 3.2 mmol) and potassium tert-butanolate (360 mg, 3.2 mmol) are added, and the resulting mixture is stirred at RT for 48 h and another 6 h at 100° C. The vola-tiles are removed under reduced pressure. The residue is taken up in water, and the solid is filtered off and purified by column chromatography (ethyl acetate/isohexane 5:2) The isolated product is washed with isohexane and dried under vacuum. Yield: 112 mg (0.09 mmol, 22%). .sup.1H-NMR (CDCl.sub.3, 300 MHz): δ=8.50 (s, 2H), 7.89 (d, 2H), 7.58 (dd, 6H), 7.54-7.29 (m, 14H), 7.29-7.22 (m, 4H), 7.08-6.99 (m, 6H), 6.87-6.79 (m, 2H), 5.86 (d, 2H), 2.30 (s, 6H) ppm. .sup.13C-NMR (CDCl.sub.3, 75 MHz): δ=160.6, 156.9, 155.5, 152.9, 151.6, 142.7, 132.2, 130.4, 130.0, 128.6, 128.1, 126.0, 124.9, 124.1, 123.1, 122.8, 122.1, 121.1, 120.1, 119.6, 116.8, 115.7, 111.4, 35.3 ppm. M.p.=251-252° C.

[0513] Photoluminescence (2% in PMMA matrix): λ.sub.max=561 nm, CIE: (0.44; 0.55); QY=82%, τ.sub.0=1.8 ρs. Neat film: λ.sub.max=589 nm, CIE: (0.55; 0.47).

[0514] In FIG. 1a, the crystal structure of complex (Iaa) ist shown.

II.2 Synthesis of Complex (Iab)

[0515] A mixture of 1,3-diphenyl-1H-benzimidazolium tetrafluoroborate (573 mg, 1.6 mmol) and silver(I) oxide (185 mg, 0.8 mmol) in dry DMF (40 mL) is stirred under argon in the dark at 60° C. for 20 h. Dichloro(1,5-cyclooctadiene)platinum(II) (599 mg, 1.6 mmol) is added at RT and the mixture is stirred at RT for 48 h and then at 130° C. for another 24 h. After cooling to RT, N,N-diphenylformamidine (1.26 g, 6.4 mmol) and potassium tert-butanolate (718 mg, 6.4 mmol) are added, and the resulting mixture is stirred at RT for 48 h and another 20 h at 100° C. The vola-tiles are removed under reduced pressure. The residue is taken up in water, and the solid is filtered off and purified by column chromatography (dichloromethane/isohexane 1:1) The isolated product is dried under vacuum. Yield: 299 mg (0.2 mmol, 28%). .sup.1H-NMR (DMSO-d.sub.6, 600 MHz): δ=7.90 (d, 2H), 7.67 (t, 2H), 7.62 (d, 2H), 7.54 (d, 4H), 7.49 (s, 2H), 7.45 (d, 2H), 7.35-7.25 (m, 6H), 7.22 (t, 2H), 7.13 (d, 4H), 7.09 (t, 4H), 6.95 (t, 4H), 6.87-6.76 (m, 6H), 6.73 (t, 2H), 6.66 (d, 2H), 6.22 (t, 2H), 5.63 (t, 2H) ppm. .sup.13C-NMR (DMSO-d.sub.6, 151 MHz): δ=157, 134.8, 130.1, 129.1, 128.8, 128.4, 127.7, 127.4, 126.6, 124.0, 123.2, 122.9, 122.4, 121.9, 121.8, 121.5, 121.4, 121.14, 121.10, 111.4, 111.3, 110.9 ppm.

[0516] Photoluminescence (2% in PMMA matrix): λ.sub.max=596 nm, CIE: (0.56; 0.43); QY=82%, τ.sub.0=2.1 ρs. Neat film: λ.sub.max=618 nm, CIE: (0.60; 0.38).

[0517] In FIG. 1b, the crystal structure of complex (Iab) ist shown.

III Application Examples

[0518] The ITO substrate used as the anode is cleaned first with commercial detergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for a further 25 minutes. This treatment also improves the hole injection properties of the ITO. Next, the hole injection layer AJ20-1000 from Plexcore is spun on from solution.

[0519] Thereafter, a mixture of complex (emitter) Iaa (10% by wt.) and compound

##STR00146##

or compound

##STR00147##

(90% by wt.) is applied by spin coating with a thickness of 40 nm, the latter compounds functioning as matrix materials.

[0520] Subsequently, the optional HBL (hole blocking layer) (5 nm layer thickness) and the ETL (electron transport layer) are applied by vapor deposition. As an electron incjetion layer, KF is applied by vapor deposition with a thickness of 4 nm and finally a 100 nm-thick Al electrode. All components are adhesive-bonded to a glass lid in an inert nitrogen atmosphere.

TABLE-US-00002 Example Host HBL ETL γ.sub.max CIE(x;y) Device 1 Host-2 BPhen (40 nm) 568 nm 0.46;0.53 Device 2 Host-1 Host-1 ETM-1: Liq (1:1, 35 nm) 566 nm 0.45;0.54 [00148]

[0521] In FIG. 2, the EL (electroluminescence) spectrum of device 2 is shown (y-axis: intensity in arbitrary units; x-axis: wavelength in nm).