Electroluminescent Imidazo-Quinoxaline Carbene Metal Complexes

Abstract

Metal carbene complexes comprising at least one imidazo-quinoxaline ligand, organic electronic devices, especially OLEDs (Organic Light-Emitting Diodes) which comprise such complexes, a light-emitting layer comprising at least one inventive metal carbene complex, an apparatus selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, the use of such a metal carbene complex for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices and a process for preparing such metal carbene complexes.

Claims

1. A metal carbene complex, comprising at least one ligand of formula (A) ##STR00792## wherein Z is NR.sup.x, O or S; R.sup.x is ##STR00793## R.sup.1, R.sup.2, R.sup.3 and R.sup.4 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 3 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; or a —NR.sup.65-heteroaryl group, comprising 3 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.1 and R.sup.2, R.sup.2 and R.sup.3 or R.sup.3 and R.sup.4 form together a ring ##STR00794## wherein A.sup.21, A.sup.21′, A.sup.22, A.sup.22′, A.sup.23, A.sup.23′, A.sup.24′ and A.sup.24 are independently of each other hydrogen, a C.sub.1-C.sub.4alkyl group, a C.sub.3-C.sub.6cycloalkyl group, or a fluoroC.sub.1-C.sub.4alkyl group; 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 3 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; R.sup.7, R.sup.8, R.sup.9, R.sup.27 and R.sup.28 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 3 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; in addition to the groups mentioned above, R.sup.8 may be a —NR.sup.65—C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; or a —NR.sup.65-heteroaryl group comprising 3 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; or R.sup.5 and R.sup.6 and/or R.sup.8 and R.sup.9 together form a group of formula ##STR00795## wherein Z is N or CR″′, wherein 0 or 1 Z is N, X is O, S, NR.sup.75 or CR.sup.73R.sup.74; R′″ is C.sub.1-C.sub.8alkyl; a is 0, 1 or 2; 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, 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.1-C.sub.8haloalkyl group, or a C.sub.1-C.sub.8alkyl group; 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 3 to 11 ring atoms, interrupted by at least one of O, S, N and NR.sup.65; or a heteroaryl group comprising 3 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; or a group of formula ##STR00796## wherein R.sup.a is hydrogen, 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.e is hydrogen, 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.3-C.sub.10heterocycloalkyl radical 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 C.sub.2-C.sub.30heteroaryl group, 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 ##STR00797## wherein Z is N or CR′″, wherein 0 or 1 Z is N, X is O, S, NR.sup.75 or CR.sup.73R.sup.74 R″′ is C.sub.1-C.sub.8alkyl, a is 0, 1 or 2; R.sup.63 and R.sup.64 are independently of each other hydrogen; 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 hydrogen, 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 hydrogen, 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 hydrogen; 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 hydrogen, 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 hydrogen, C.sub.1-C.sub.25alkyl which is interrupted by O, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl, which is substituted by C.sub.1-C.sub.18alkyl; 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 3 to 11 ring atoms, which can optionally be substituted by C.sub.1-C.sub.18alkyl; and ˜ is a bonding site to the metal, wherein the metal is selected from the group consisting of Ir and Pt.

2. The metal carbene complex according to claim 1, wherein: R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other 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.12cycloalkyl 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 groups G; a heteroaryl group comprising 3 to 11 ring atoms, which can optionally be substituted by one or two groups G; or a —N(phenyl).sub.2 group, which can optionally be substituted by one or two groups G; 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; or one of R.sup.5 and R.sup.6 is a group of formula ##STR00798## wherein: R.sup.a is hydrogen, 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.e is hydrogen, 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; a C.sub.2-C.sub.30heteroaryl group, 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 ##STR00799## wherein Z is N or CR″′, wherein 0 or 1 Z is N, 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.7, 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; a C.sub.3-C.sub.12cycloalkyl group, which can optionally be substituted by E, a C.sub.6-C.sub.14aryl group, which can optionally be substituted by one or two groups G; a heteroaryl group comprising 3 to 11 ring atoms, which can optionally be substituted by one or two groups G. R.sup.27, R.sup.28 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; 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.8alkyl; 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—; and 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—.

3. The metal carbene complex according to claim 1, wherein at least one of the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is not hydrogen.

4. The metal carbene complex according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other hydrogen; a C.sub.1-C.sub.8alkyl 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 a phenyl group, which can optionally be substituted by one or two groups G; R.sup.5 and R.sup.6 are independently of each other hydrogen; a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent E; or a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or a phenyl group, which can optionally be substituted by one or two groups G; R.sup.7, R.sup.8 and R.sup.9 are independently of each other hydrogen; a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent E; or a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or a phenyl group, which can optionally be substituted by one or two groups G; R.sup.27 and R.sup.28 are hydrogen; E is CF.sub.3, C.sub.1-C.sub.8alkyl, or F; G is CF.sub.3 or C.sub.1-C.sub.8alkyl; 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.8alkyl group; or a C.sub.1-C.sub.8alkyl group, which is interrupted by —O—; and 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.8alkyl group; or a C.sub.1-C.sub.8alkyl group, which is interrupted by —O—.

5. The metal carbene complex according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other hydrogen; a C.sub.1-C.sub.8alkyl group; or a C.sub.3-C.sub.6cycloalkyl group; R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently of each other hydrogen; a C.sub.1-C.sub.8alkyl group; or a C.sub.3-C.sub.6cycloalkyl group; or one of R.sup.5 and R.sup.6 is a phenyl group, which can optionally be substituted by one or two groups G; and R.sup.27 and R.sup.28 are hydrogen.

6. The metal carbene complex according to claim 1, wherein either R.sup.2 and R.sup.3, or R.sup.1 and R.sup.4, are hydrogen.

7. The metal carbene 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.8alkyl group; or one of R.sup.5 and R.sup.6 is a phenyl group, which can optionally be substituted by one or two groups selected from CF.sub.3 or C.sub.1-C.sub.8alkyl; R.sup.7 and R.sup.9 are C.sub.1-C.sub.8alkyl; R.sup.8 is hydrogen; a C.sub.1-C.sub.8alkyl group; or a phenyl group, which can optionally be para-substituted by one group selected from CF.sub.3 or C.sub.1-C.sub.8alkyl; and R.sup.27 and R.sup.28 are hydrogen.

8. The metal carbene complex according to claim 1, wherein R.sup.5 is hydrogen; a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent selected from CF.sub.3, C.sub.1-C.sub.8alkyl and F; a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent selected from CF.sub.3, C.sub.1-C.sub.8alkyl and F; or a phenyl group, which can optionally be substituted by one or two groups selected from CF.sub.3 and C.sub.1-C.sub.8alkyl; R.sup.6 and R.sup.8 are identical and selected from the group consisting of a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent selected from CF.sub.3, C.sub.1-C.sub.8alkyl and F; a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent selected from CF.sub.3, C.sub.1-C.sub.8alkyl and F; and a phenyl group, which can optionally be substituted by one or two groups selected from CF.sub.3 and C.sub.1-C.sub.8alkyl; R.sup.7 and R.sup.9 are hydrogen; wherein R.sup.5 and R.sup.6 are not at the same time a phenyl group, which can optionally be substituted by one or two groups selected from CF.sub.3 and C.sub.1-C.sub.8alkyl; and R.sup.27 and R.sup.28 are hydrogen.

9. The metal carbene complex according to claim 1, wherein R.sup.7, R.sup.8 and R.sup.9 are hydrogen; R.sup.6 is hydrogen; and R.sup.27 and R.sup.28 are hydrogen.

10. The metal carbene complex according to claim 1, having the following formula (II) ##STR00800## wherein M is Pt or Ir; wherein if M is Ir, m is 1, 2, or 3; o is 0, 1, or 2; and the sum of m+o is 3; wherein when o=2, the ligands L may be the same or different; and when m is 2 or 3, the m carbene ligands may be the same or different; wherein if M is Pt, m is 1, or 2; o is 0, or 1; and the sum of m+o is 2; wherein when m is 2, the m carbene ligands may be the same or different; and L is a monoanionic bidentate ligand.

11. The metal carbene complex according to claim 1, wherein L is a group of formula ##STR00801## ##STR00802## ##STR00803## ##STR00804## ##STR00805## ##STR00806## ##STR00807## ##STR00808## wherein the radicals R.sup.10, R.sup.12, R.sup.13, R.sup.16, R.sup.17, R.sup.18 and R.sup.19 are—in each case—independently of each other 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 E; a heterocycloalkyl group comprising 3 to 6 ring atoms, interrupted by at least one heteroatom selected from —O—, —S— and —NR.sup.65—, optionally bearing at least one substituent E; a halogen atom; C.sub.1-C.sub.8haloalkyl; CN; or SiR.sup.80R.sup.81R.sup.82; or one radical R.sup.10 and/or one radical R.sup.12; one radical R.sup.13 and/or one radical R.sup.12; one radical R.sup.16 and/or one radical R.sup.17; one radical R.sup.18 and/or one radical R.sup.19 is a group of formula ##STR00809## wherein R.sup.a is hydrogen, 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.e is hydrogen, 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.3-C.sub.10heterocycloalkyl radical 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; a C.sub.2-C.sub.30heteroaryl group, 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 two adjacent radicals R.sup.10 and/or two adjacent radicals R.sup.12; two adjacent radicals R.sup.13 and/or two adjacent radicals R.sup.12; two adjacent radicals R.sup.16 and/or two adjacent radicals R.sup.17; or two adjacent radicals R.sup.19; or R.sup.c and R.sup.b, or R.sup.a and R.sup.b together form a group of formula ##STR00810## wherein Z is N or CR″′, wherein 0 or 1 Z is N, 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 or 1; or the radicals R.sup.11, R.sup.14, R.sup.20, R.sup.21, R.sup.22, R.sup.23 and R.sup.24 are—in each case—independently of each other 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 heteroatom selected from —O—, —S— and —NR.sup.65—, optionally bearing at least one substituent E; a C.sub.6-C.sub.14aryl group, which can optionally be substituted by one or two groups G; a heteroaryl group comprising 3 to 11 ring atoms, which can optionally be substituted by one or two groups G; or a —NR.sup.65-phenyl group, which can optionally be substituted by one or two groups G; or in the case of X-1, X-2, X-3, X-31, X-34, X-35, X-36, X-37 and X-38 CN; or two adjacent radicals R.sup.11 or two adjacent radicals R.sup.14 form together a group ##STR00811## wherein A.sup.21, A.sup.21′, A.sup.22, A.sup.22′, A.sup.23, A.sup.23′, A.sup.24′ and A.sup.24 are independently of each other hydrogen, a C.sub.1-C.sub.4alkyl group, a C.sub.3-C.sub.6cycloalkyl group, or a fluoroC.sub.1-C.sub.4alkyl group; or R.sup.25 is CH.sub.3 or ethyl or iso-propyl; R.sup.26 is a phenyl group, which can optionally be substituted by one or two groups selected from CF.sub.3 and C.sub.1-C.sub.8alkyl; or R.sup.26 is CH.sub.3; or iso-propyl; D is —S—, —O—, or —NR.sup.65—; E is —OR.sup.69, —CN, CF.sub.3, C.sub.1-C.sub.8alkyl or F; G is —OR.sup.69, —CN, CF.sub.3 or C.sub.1-C.sub.8alkyl; 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—; and A.sup.1 is C.sub.6-C.sub.10aryl; or two adjacent groups A.sup.1 together form a group ##STR00812## wherein R.sup.f, R.sup.g, R.sup.h and R.sup.1 are independently of each other hydrogen or C.sub.1-C.sub.8alkyl; Q.sup.1 and Q.sup.2 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, or C.sub.6-C.sub.18aryl; w and x are independently of each other 0, 1 or 2; z is 0, 1, 2 or 3; y, y′, y″, u, and v are independently of each other 0, 1 or 2; y′″ is 0 or 1; p, q, r, s, t, t′, and t″ are independently of each other 0, 1, 2, 3 or 4; and r′ is 0, 1, or 2.

12. The metal carbene complex according to claim 1, wherein the metal is Ir.

13. The metal carbene complex according to claim 12, selected from the group consisting of formulae IIa, IIb, IIc, IId, IIe, IIf, Iig, and IIh; ##STR00813## ##STR00814## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other—in each case—hydrogen; a C.sub.1-C.sub.8alkyl 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; or a phenyl group, which can optionally be substituted by one or two groups G; R.sup.5 and R.sup.6 are independently of each other—in each case—hydrogen; a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; or a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or a phenyl group, which can optionally be substituted by one or two groups G; R.sup.8 and R.sup.9 are independently of each other hydrogen; a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; or a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or a phenyl group, which can optionally be substituted by one or two groups G; D is —S— or —O—; E is —OR.sup.69, —CN, CF.sub.3, C.sub.1-C.sub.8alkyl or F; G is —OR.sup.69, —CN, CF.sub.3 or C.sub.1-C.sub.8alkyl; 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.8alkyl group; or a C.sub.1-C.sub.8alkyl group, which is interrupted by —O—; L is a monoanionic bidentate ligand; m is 1, 2, or 3; o is 0, 1, or 2; and the sum of m+o is 3; wherein when o=2, the ligands L may be the same or different; and when m is 2 or 3, the m carbene ligands may be the same or different.

14. The metal carbene complex according to claim 13, selected from the group consisting of formulae II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, II-9, II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-17, II-18, II-19, II-20, II-21, II-22, II-23, II-24, II-25, II-26, II-27, II-28, II-29, II-30, II-31, II-32, II-33, II-34, II-35, II-36, II-37, II-38, II-39, II-40, II-41, II-42, II-43, II-44, II-45, II-46, II-47, II-48, II-49, II-50, II-51, II-52, II-53, II-54, II-55, II-56, II-57, II-58, II-59, II-60, II-61, II-62, II-63, II-64, II-65, II-66, II-67, II-68, II-69, II-70, II-71, II-72, II-73, and II-74; ##STR00815## ##STR00816## ##STR00817## ##STR00818## ##STR00819## ##STR00820## ##STR00821## ##STR00822## ##STR00823## ##STR00824## ##STR00825## ##STR00826## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other—in each case—hydrogen, a C.sub.1-C.sub.8alkyl 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; or a phenyl group, which can optionally be substituted by one or two groups G; R.sup.5 and R.sup.6 are independently of each other—in each case—hydrogen, a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; or a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or a phenyl group, which can optionally be substituted by one or two groups G; R.sup.8 and R.sup.9 are independently of each other—in each case—hydrogen, a C.sub.1-C.sub.8alkyl group, which can optionally be substituted by at least one substituent E and/or interrupted by D; or a C.sub.3-C.sub.6cycloalkyl group, which can optionally be substituted by at least one substituent E; or a phenyl group, which can optionally be substituted by one or two groups G; D is —S— or —O—; E is —OR.sup.69, —CN, CF.sub.3, C.sub.1-C.sub.8alkyl or F; G is —OR.sup.69, —CN, CF.sub.3 or C.sub.1-C.sub.8alkyl; 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.8alkyl group; or a C.sub.1-C.sub.8alkyl group, which is interrupted by —O—; m is 2 or 1; wherein when m is 2, the two ligands are identical or different; o is 1 or 2; wherein when o is 2, the two ligands are identical or different; and the sum of m+o is 3.

15. An organic electronic device, comprising at least one metal carbene complex of claim 1.

16. The organic electronic device according to claim 15, wherein the organic electronic device is selected from an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic field-effect transistor (OFET) and a light-emitting electrochemical cell (LEEC).

17. A light-emitting layer comprising at least one metal carbene complex according to claim 1.

18. The light-emitting layer according to claim 17, comprising at least one metal carbene complex of claim 1 and at least one host material.

19. An apparatus selected from the group consisting of a stationary visual display unit; an illumination unit; a keyboard; an item of clothing; furniture; and wallpaper, wherein the apparatus comprises the organic electronic device according to claim 15.

20. A device selected from the group consisting of an electrophotographic photoreceptor, a photoelectric converter, an organic solar cell (organic photovoltaic), a switching element, an organic light emitting field effect transistor (OLEFET), an image sensor, a dye laser, and an electroluminescent device, wherein the device comprises the metal carbene complex of claim 1.

21. A process for preparing a metal carbene complex according to claim 1, wherein the process comprises the step of contacting suitable compounds comprising Ir with appropriate ligands or ligand precursors.

22. A process for preparing a metal carbene complex according to claim 1, comprising at least one ligand of formula (I′) ##STR00827## wherein: R.sup.5′ is 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 C.sub.6-C.sub.14aryl group, which can optionally be substituted by at least one substituent G; a —N(C.sub.6-C.sub.14aryl).sub.2 group, which can optionally be substituted by at least one substituent G; or a heteroaryl group comprising 3 to 11 ring atoms, which can optionally be substituted by at least one substituent G, interrupted by at least one of O, S and N; comprising the step of reacting a metal carbene complex comprising at least one ligand of formula (III) ##STR00828## with a compound of formula (IV) corresponding to the respective Y-substituted residue R.sup.5′: R.sup.5′—Y (IV) wherein X.sup.1 is Cl, Br, or I; Y is —B(OH).sub.2, —B(OY.sup.1).sub.2, ##STR00829## wherein Y.sup.1 is a C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10alkylene group, such as —CY.sup.3Y.sup.4—CY.sup.5Y.sup.6—, or —CY.sup.7Y.sup.8—CY.sup.9Y.sup.10—CY.sup.11Y.sup.12—, wherein Y.sup.3 , Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7, Y.sup.8, Y.sup.9, Y.sup.10, Y.sup.11 and Y.sup.12 are independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl group, and Y.sup.13 and Y.sup.14 are independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl group; or Y is —SnR.sup.307R.sup.308R.sup.309, wherein R.sup.307, R.sup.308 and R.sup.309 are identical or different and are hydrogen or C.sub.1-C.sub.6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched; ZnR.sup.310R.sup.311, wherein R.sup.310 is halogen and R.sup.311 is a C.sub.1-C.sub.10alkyl group, a C.sub.6-C.sub.12aryl group, or C.sub.1-C.sub.10alkenyl group; or SiR.sup.312R.sup.313R.sup.314, wherein R.sup.312, R.sup.313 and R.sup.314 are identical or different and are halogen or C.sub.1-C.sub.6alkyl, and wherein the metal is selected from Ir and Pt.

23. The metal carbene complex according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.27 and R.sup.29 are hydrogen.

24. The metal carbene complex according to claim 1, wherein the metal carbene complex has one of the following formulae: ##STR00830## ##STR00831## ##STR00832## ##STR00833## ##STR00834## ##STR00835## ##STR00836## ##STR00837## ##STR00838## ##STR00839## ##STR00840## ##STR00841## ##STR00842##

Description

FIGURE

[0837] FIG. 1 shows a comparison of the emission spectrum of OLED device 3 comprising inventive complex (IV) compared with the emission spectrum of OLED device 3 comprising comparative complex (CC-3).

[0838] In FIG. 1:

[0839] The Y-axis shows the EL intensity in arbitrary units (a.u.) and the X-axis shows the wavelength in nm. The dotted line shows the emission spectrum of the OLED comprising inventive complex (IV) and the continuous line shows the emission spectrum of the OLED comprising comparative complex (CC-3).