Method for the separation of enantiomeric mixtures from metal complexes

Abstract

The present invention relates to processes for separating mixtures containing enantiomers of metal complexes with aromatic and/or heteroaromatic ligands, to metal complexes and to electronic devices, especially organic electroluminescent devices, comprising these metal complexes.

Claims

1. A process for separating mixtures containing enantiomers of metal complexes with aromatic and/or heteroaromatic ligands, comprising the steps of: A) providing a mixture of reactive metal complexes, wherein the mixture comprises at least two enantiomers of the reactive metal complexes; B) reacting the mixture provided in step A) with an optically active boron compound to obtain a diastereomer mixture; and C) separating the diastereomer mixture obtained in step B).

2. The process of claim 1, wherein a mixture of metal complexes is used, wherein the reactive metal complexes are reactive metal complexes of formula (1):
Ir(L).sub.n(L′).sub.m  (1) wherein L is the same or different in each instance and is a bidentate ligand; L′ is the same or different in each instance and is a ligand; n is 1, 2, or 3; and m is 0, 1, 2, 3, or 4; and wherein two or more ligands L are optionally joined together or L is optionally joined to L′ via a single bond or a bivalent or trivalent bridge so as to define a tridentate, tetradentate, pentadentate, or hexadentate ligand system.

3. The process of claim 2, wherein the reactive metal complexes of formula (1) comprise a substructure M(L).sub.n of formula (2): ##STR00185## wherein CyC is the same or different in each instance and is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene or azafluorene group, each of which coordinates to Ir via a carbon atom and each of which is optionally substituted by one or more R radicals and which is bonded to CyD via a covalent bond; CyD is the same or different in each instance and is a heteroaryl group having 5 to 18 aromatic ring atoms and coordinates to Ir via an uncharged nitrogen atom or via a carbene carbon atom and which is optionally substituted by one or more R radicals and which is bonded to CyC via a covalent bond R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1)2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR.sup.1, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, C(═O)OR.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F, and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic ring system; and n is 1, 2, or 3; wherein two or more ligands L are optionally joined to one another via a single bond or a bivalent or trivalent bridge so as to define a tridentate, tetradentate, pentadentate, or hexadentate ligand system; and wherein a substituent optionally additionally coordinates to Ir.

4. The process of claim 1, wherein the metal complex has one, two, or three bidentate ligands, wherein the bidentate ligands are the same or different in each instance and have one carbon atom and one nitrogen atom or two carbon atoms or two nitrogen atoms or two oxygen atoms or one oxygen atom and one nitrogen atom as coordinating atoms.

5. The process of claim 2, wherein at least one of the bidentate ligands is selected from the group consisting of structures of formulae (L-1-1), (L-1-2), (L-2-1), (L-2-2), (L-2-3), and (L-2-4): ##STR00186## wherein * denotes the position of coordination to the metal; X is the same or different in each instance and is CR or N, with the proviso that not more than one X symbol per cycle is N, and wherein X is C if the ligand at this position is bonded to a bridge; and R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted “o”; and/or wherein at least one of the bidentate ligands is selected from the group consisting of structures of formulae (L-3) through (L-30): ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## wherein * denotes the position of coordination to the metal; X is the same or different in each instance and is CR or N, with the proviso that not more than one X symbol per cycle is N, wherein X is C if the ligand at this position is bonded to a bridge; and R and R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C═C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted “o”; and/or wherein at least one of the bidentate ligands is selected from the group consisting of structures of formulae (L-31) and (L-32): ##STR00194## wherein * denotes the position of coordination to the metal; X is the same or different in each instance and is CR or N, with the proviso that not more than one X symbol per cycle is N, wherein X is C if the ligand at this position is bonded to a bridge; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted “o”; and/or wherein at least one of the bidentate ligands is selected from the group consisting of structures of formulae (L-39) through (L-42): ##STR00195## wherein the ligands (L-39), (L-40), and (L-41) each coordinate to the metal via the nitrogen atom and the negatively charged oxygen atom and the sub-ligand (L-42) via the two oxygen atoms; X is the same or different in each instance and is CR or N, with the proviso that not more than one symbol X per cycle is N, where X is C if the ligand is bonded to a bridge at this position; and R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more RI radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more RI radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted “o, wherein X is C if the ligand is bonded to a bridge at this position, or, in formula (L-42), the carbon atom optionally has a substituent R if the ligand is not bonded to a bridge at this position.

6. The process of claim 1, wherein the metal complex has at least one ligand having two substituents R and/or two substituents R.sup.1 which are bonded to adjacent carbon atoms and together define a ring of one of formulae (RI-1) through (RI-8): ##STR00196## wherein R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, C(═O)OR.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; the dotted bonds denote the linkage of the two carbon atoms in the ligand; A.sup.1 and A.sup.3 are the same or different in each instance and are C(R.sup.3).sub.2, O, S, NR.sup.3, or C(═O); A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(═O); A.sup.4 and A.sup.5 are the same or different in each instance and is CR.sup.1 or N; A.sup.6 and A.sup.7 are the same or different in each instance and is an alkylene group having 2 or 3 carbon atoms, in which one carbon atom is optionally replaced by oxygen and which is optionally substituted by one or more R.sup.1 radicals; with the proviso that, in A.sup.4-A.sup.6-A.sup.5 or A.sup.4-A.sup.7-A.sup.5, no two heteroatoms are bonded directly to one another, G is an alkylene group having 1, 2, or 3 carbon atoms and is optionally substituted by one or more R.sup.2 radicals, —CR.sup.2═CR.sup.2— or an ortho-bonded arylene or heteroarylene group having 5 to 14 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; R.sup.3 is the same or different in each instance and is H, F, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, wherein the alkyl or alkoxy group is optionally substituted in each case by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two R.sup.3 radicals bonded to the same carbon atom together optionally define an aliphatic or aromatic ring system so as to define a spiro system; and wherein R.sup.3 together with an adjacent R or R.sup.1 radical optionally defines an aliphatic ring system; and R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F, and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic ring system; with the proviso that no two heteroatoms in these groups are bonded directly to one another and no two C═O groups are bonded directly to one another.

7. The process of claim 1, wherein a mixture of reactive metal complexes is used, wherein the reactive metal complexes are reactive metal complexes of formula:
Ir(L).sub.n(L′).sub.m  (1a) L is the same or different in each instance and is a bidentate ligand; L′ is the same or different in each instance and is a ligand; n is 1, 2, or 3; and m is 0, 1, 2, 3, or 4; and the ligands L and/or L′ are bonded via a bridge, wherein a substructure of formula (2) is optionally formed: ##STR00197## wherein CyC is the same or different in each instance and is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene or azafluorene group, each of which coordinates to Ir via a carbon atom and each of which is optionally substituted by one or more R radicals and which is bonded to CyD via a covalent bond; CyD is the same or different in each instance and is a heteroaryl group having 5 to 18 aromatic ring atoms and coordinates to Ir via an uncharged nitrogen atom or via a carbene carbon atom and which is optionally substituted by one or more R radicals and which is bonded to CyC via a covalent bond R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, C(═O)OR.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F, and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic ring system; and n is 1, 2, or 3; wherein two or more ligands L are optionally joined to one another via a single bond or a bivalent or trivalent bridge so as to define a tridentate, tetradentate, pentadentate, or hexadentate ligand system; and wherein a substituent optionally additionally coordinates to Ir.

8. The process of claim 7, wherein the bridge via which the ligands are bonded is a bridge of formula (3) ##STR00198## wherein the dotted bond denotes the bond of the ligands to this structure; X.sup.1 is the same or different in each instance and is C, which is optionally substituted, or N; X.sup.2 is the same or different in each instance and is C, which is optionally substituted, or N; or two adjacent X.sup.2 groups together are N, which are optionally substituted, O, or S, so as to define a five-membered ring; or two adjacent X.sup.2 groups together are C, which are optionally substituted, or N when one of the X.sup.3 groups in the cycle is N, so as to define a five-membered ring; with the proviso that not more than two adjacent X.sup.2 groups in each ring are N; and wherein any substituents may optionally define a ring system with one another or with substituents bonded to X.sup.1; X.sup.3 is C at each instance in one cycle or one X3 group is N and the other X.sup.3 group in the same cycle is C, where the X.sup.3 groups in the three cycles may be selected independently; with the proviso that two adjacent X.sup.2 groups together are C which may also be substituted or N when one of the X.sup.3 groups in the cycle is N; or wherein the bridge via which the ligands are bonded is a bridge of formula (4): ##STR00199## wherein the dotted bond denotes the bond of the ligands to this structure; X.sup.1 is the same or different in each instance and is C, which is optionally substituted, or N; X.sup.3 is the same or different in each instance and is CR or N, with the proviso that no two nitrogen atoms are bonded directly to one another; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; or wherein the bridge via which the ligands are bonded is a bridge of formula (5) ##STR00200## wherein the dotted bond denotes the bond of the ligands to this structure; X.sup.1 is the same or different in each instance and is C, which is optionally substituted, or N; A is the same or different in each instance and is selected from the group consisting of —O—C(═O)—, —NR—C(═O)—, and —CR.sub.2—CR.sub.2—, wherein the R radical bonded to the nitrogen atom is not H or D; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; or wherein the bridge via which the ligands are bonded is a bridge of formulae (6), (7), or (8) ##STR00201## wherein the dotted bond denotes the bond of the ligands to this structure; R is as defined above; X.sup.2 and X.sup.3 in formula (6) have the definitions specified for X.sup.2 and X.sup.3 in formula (3); X.sup.3 in formula (7) has the definition specified for X.sup.3 in formula (4); wherein the three bidentate ligands, apart from via the bridges of formulae (3) through (8), is optionally ring-closed via a further bridge to form a cryptate.

9. The process of claim 1, wherein the optically active boron compound is a boron compound of formula (BE-1): ##STR00202## wherein Z.sup.a is H, D, OR, halogen, or B(R).sub.2; Z.sup.b and Z.sub.c are the same or different in each instance and is OR, N(R).sub.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group are in each case optionally substituted by one or more R radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by RC═CR, C≡C, Si(R).sub.2, C═O, NR, O, S, COOR, or CONR, and wherein the R radicals optionally together define a ring system; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)OR.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; and wherein at least one of the Z.sup.b or Z.sup.c radicals comprises a chiral center.

10. The process of claim 9, wherein the optically active boron compound is a compound of formula (BE-2) or (BE 3): ##STR00203## W is the same or different in each instance and is NR, O, or S; R.sup.a, R.sup.b, R.sup.c, and R.sup.d are the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)RI, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein each alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R.sup.a, R.sup.b, R.sup.c, and/or R.sup.d radicals together optionally define a ring system; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, C(═O)ORI, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; and R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, C(═O)OR.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2 a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl groups are optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system.

11. A metal complex obtained by the process of claim 1.

12. A metal complex of formula (1b)
Ir(L).sub.n(L′).sub.m  (1b) wherein L is the same or different in each instance and is a bidentate ligand; L′ is the same or different in each instance and is a ligand; n is 1, 2, or 3; and m is 0, 1, 2, 3, or 4; and wherein two or more ligands L are optionally joined together or L is optionally joined to L′ via a single bond or a bivalent or trivalent bridge so as to define a tridentate, tetradentate, pentadentate, or hexadentate ligand system; and wherein at least one of the ligands L and/or L′ comprises a boron-containing substituent having a chiral center.

13. The metal complex of claim 12, wherein the boron-containing substituent having a chiral center is a boron-containing substituent of formula (BS-1): ##STR00204## wherein Z.sup.b and Z.sup.c are the same or different in each instance and is OR, N(R).sub.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group are in each case optionally substituted by one or more R radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by RC═CR, C≡C, Si(R).sub.2, C═O, NR, O, S, COOR, or CONR, and wherein the R radicals optionally together define a ring system; and the dotted line denotes the bond to the ligand.

14. An oligomer, polymer, or dendrimer containing one or more metal complexes according to claim 12, wherein, rather than a hydrogen atom or a substituent, one or more bonds of the metal complex to the polymer, oligomer, or dendrimer are present.

15. A formulation comprising at least one metal complex of claim 12 and at least one solvent.

16. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 14 at least one solvent.

17. A process for preparing optically active transition metal complexes comprising converting a composition obtained after step C) of the process of claim 1 in a coupling reaction with elimination of boron compounds.

18. An electronic device comprising at least one metal complex of claim 12.

19. The electronic device of claim 18, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, oxygen sensors, oxygen sensitizers, and organic laser diodes.

20. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 14.

21. The electronic device of claim 20, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, oxygen sensors, oxygen sensitizers, and organic laser diodes.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

A: Synthesis of Hexadentate Ligands

Example L1

(2) ##STR00129##

(3) A mixture of 54.1 g (100 mmol) of 1,3,5-tris(2-bromophenyl)benzene [380626-56-2], 98.4 g (350 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine [879291-27-7], 106.0 g (1 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphino)palladium(0), 750 ml of toluene, 200 ml of ethanol and 500 ml of water is heated under reflux with very good stirring for 24 h. After 24 h, 300 ml of 5% by weight aqueous acetylcysteine solution are added, the mixture is stirred under reflux for a further 10 h and allowed to cool, the aqueous phase is removed and the organic phase is concentrated to dryness. After the organic phase from the Suzuki coupling has been concentrated, the brown foam is taken up in 300 ml of a mixture of dichloromethane:ethyl acetate (8:1, v/v) and filtered through a silica gel bed in the form of a dichloromethane:ethyl acetate slurry (8:1, v/v) (diameter 15 cm, length 20 cm), in order to remove brown components. After concentration, the remaining foam is recrystallized from 800 ml of ethyl acetate with addition of 400 ml of methanol at boiling and then for a second time from 1000 ml of pure ethyl acetate and then subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.−5 mbar, T 280° C.). Yield: 50.6 g (66 mmol), 66%. Purity: about 99.7% by .sup.1H NMR.

Example L2

(4) ##STR00130##

(5) Ligand L2 can be prepared analogously. Rather than 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine [879291-27-7], 2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]pyridine [908350-80-1] is used. Yield: 56.0 g (73 mmol), 73%. Purity: about 99.5% by .sup.1H NMR.

Example L3

(6) Synthon S1:

(7) ##STR00131##

(8) A mixture of 29.0 g (100 mmol) of 2-(4-bromophenyl)-4-tert-butylpyridine [1246851-70-6], 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 1.5 g (2 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM [95464-05-4], 200 g of glass beads (diameter 3 mm), 700 ml of 1,4-dioxane and 700 ml of toluene is heated under reflux for 16 h. After cooling, the suspension is filtered through a Celite bed and the solvent is removed under reduced pressure. The black residue is digested with 1000 ml of hot n-heptane and filtered through a Celite bed while still hot, then concentrated to about 200 ml, in the course of which the product begins to crystallize. The crystallization is completed in a refrigerator overnight, and the crystals are filtered off and washed with a little n-heptane. A second product fraction can be obtained from the mother liquor. Yield: 26.6 g (79 mmol) 79%. Purity: about 95% by .sup.1H NMR

(9) Ligand L3:

(10) ##STR00132##

(11) Ligand L3 can be prepared analogously to ligand L1. Rather than 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine [879291-27-7], synthon S1 is used. Yield: 65.4 g (70 mmol), 70%. Purity: about 99% by .sup.1H NMR.

B: Organometallic Synthons

1. Metal Complex Synthons MS Known from the Literature

(12) ##STR00133##

2. Synthesis of the Metal Complexes Ir(L1)

Example Ir(L1)

(13) ##STR00134##

(14) A mixture of 7.66 g (10 mmol) of ligand L1, 4.90 g (10 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 120 g of hydroquinone [123-31-9] is initially charged in a 500 ml two-neck round-bottom flask with a glass-sheathed magnetic bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanketing. The flask is placed in a metal heating bath. The apparatus is purged with argon from the top via the argon blanketing system for 15 min, allowing the argon to flow out of the side neck of the two-neck flask. Through the side neck of the two-neck flask, a glass-sheathed Pt-100 thermocouple is introduced into the flask and the end is positioned just above the magnetic stirrer bar. Then the apparatus is thermally insulated with several loose windings of domestic aluminium foil, the insulation being run up to the middle of the riser tube of the water separator. Then the apparatus is heated rapidly with a heated laboratory stirrer system to 250-260° C., measured with the Pt-100 thermal sensor which dips into the molten stirred reaction mixture. Over the next 1.5 h, the reaction mixture is kept at 250-260° C., in the course of which a small amount of condensate is distilled off and collects in the water separator. After cooling, the melt cake is mechanically comminuted and extracted by boiling with 500 ml of methanol. The beige suspension thus obtained is filtered through a double-ended frit, and the beige solid is washed once with 50 ml of methanol and then dried under reduced pressure. Crude yield: quantitative. The solid thus obtained is dissolved in 1500 ml of dichloromethane and filtered through about 1 kg of silica gel in the form of a dichloromethane slurry (column diameter about 18 cm) with exclusion of air in the dark, leaving dark-coloured components at the start. The core fraction is cut out and substantially concentrated on a rotary evaporator, with simultaneous continuous dropwise addition of MeOH until crystallization. After removal with suction, washing with a little MeOH and drying under reduced pressure, the yellow product is purified further by continuous hot extraction three times with toluene:acetonitrile (3:1, v/v) and hot extraction five times with toluene (amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Yield: 8.52 g (8.9 mmol), 89%. Purity: >99.9% by HPLC.

Example Ir(L2)

(15) ##STR00135##

(16) Ir(L2) can be prepared analogously using L2 rather than L1.

(17) Purification is effected by recrystallization from NMP three times with addition of methanol in the course of cooling of the solution. Yield: 8.04 g (8.4 mmol), 84%. Purity: >99.7% by HPLC.

Example Ir(L3)

(18) ##STR00136##

(19) Ir(L3) can be prepared analogously using L3 rather than L1.

(20) Purification is effected by hot extraction from toluene five times. Yield: 8.09 g (7.2 mmol), 72%. Purity: >99.7% by HPLC.

3. Halogenation of the Metal Complexes Ir(L1)

(21) General Procedure:

(22) To a solution or suspension of 10 mmol of the complex in 500 ml to 2000 ml of dichloromethane according to the solubility of the metal complexes are added, in the dark and with exclusion of air, at −30 to +30° C., 30-40 mmol of N-bromosuccinimide, and the mixture is stirred for 20 h. Complexes of sparing solubility in DCM may also be converted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at elevated temperature. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 ml of methanol with addition of 5 ml of hydrazine hydrate, and the solids are filtered off with suction, washed three times with about 30 ml of methanol and then dried under reduced pressure.

(23) For the preparation of mono- and dibrominated metal complexes, the procedure is analogous to the process described above, except that 10 mmol of N-bromosuccinimide are used rather than 30-40 mmol of N-bromosuccinimide for the preparation of the monobrominated metal complexes, and 20 mmol of N-bromosuccinimide for the preparation of the dibrominated metal complexes. The crude product is purified by chromatography (for example on an automated column system from Axel Semrau).

Example Ir(L1-3Br)

(24) ##STR00137##

(25) To a suspension, stirred at 0° C., of 9.6 g (10 mmol) of Ir(L1) in 2000 ml of DCM are added 7.1 g (40 mmol) of N-bromosuccinimide all at once and then the mixture is stirred for a further 20 h. After removing about 1900 ml of the DCM under reduced pressure, 100 ml of methanol and 5 ml of hydrazine hydrate are added to the yellow suspension, which is boiled while stirring, and the solids are filtered off with suction, washed three times with about 30 ml of methanol and then dried under reduced pressure. Yield: 11.3 g (9.5 mmol), 95%; purity: >99.0% by NMR.

(26) In an analogous manner, it is possible to prepare the following complexes:

(27) TABLE-US-00001 Ex. Reactant > brominated complex Yield Ir(L2-3Br) 93% Ir(L3-3Br) 95% Ir(L2-Br) 0 24% Ir(L3-2Br) 26%

4. Borylation of the Halogenated Complexes with Subsequent Chromatographic Separation of the Diastereomers Formed; General Procedure

(28) Variant 1:

(29) In a 250 ml two-neck flask with reflux condenser, magnetic stirrer bar, heating bath and argon connection, 5 mmol of a tribrominated metal complex, 30 mmol of bis[(+)-pinanediolato]diboron [230299-05-5], 45 mmol of potassium acetate [127-08-2] and 0.45 mmol of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium (II) [95464-05-4] are weighed out, and 100 ml of 1,4-dioxane are added. The reaction mixture is inertized with argon and stirred under reflux for 24-48 hours. After cooling, the reaction solution is filtered through Celite, and the Celite is rinsed with 2×50 ml of 1,4-dioxane. Subsequently, the filtrate is concentrated on a rotary evaporator and the remaining residue is worked up by extraction with DCM and water. The organic phase is removed and washed with saturated sodium chloride solution. 50 ml of ethanol are added to the organic phase, and then the dichloromethane is evaporated off on a rotary evaporator. The precipitated solids are filtered off with suction, washed twice with 10 ml each time of ethanol and dried under reduced pressure. Subsequently, the 1:1 mixture of the diastereomers obtained is separated by means of chromatographic methods. The respective product is referred to as Ir(Lx-3boron-(+)) or MSx-3boron-(+).

(30) Variant 2:

(31) In a 250 ml two-neck flask with reflux condenser, magnetic stirrer bar, heating bath and argon connection, 5 mmol of a tribrominated metal complex, 30 mmol of bis(diethyl-D-tartrate glycolato)diboron [312693-46-2], 45 mmol of potassium acetate [127-08-2] and 0.45 mmol of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium (II) [95464-05-4] are weighed out, and 100 ml of 1,4-dioxane are added. The reaction mixture is inertized with argon and stirred under reflux for 24-48 hours. After cooling, the reaction solution is filtered through Celite, and the Celite is rinsed with 2×50 ml of 1,4-dioxane. Subsequently, the filtrate is concentrated on a rotary evaporator and the remaining residue is worked up by extraction with DCM and water. The organic phase is removed and washed with saturated sodium chloride solution. 50 ml of ethanol are then added to the organic phase, and then the dichloromethane is evaporated off on a rotary evaporator. The precipitated solids are filtered off with suction, washed twice with 10 ml each time of ethanol and then dried under reduced pressure. Subsequently, the 1:1 mixture of the diastereomers obtained is separated by means of chromatographic methods. The respective product is referred to as Ir(Lx-3boron-D) or MSx-3-boron-D.

(32) Variant 3:

(33) In a 250 ml two-neck flask with reflux condenser, magnetic stirrer bar, heating bath and argon connection, 5 mmol of a tribrominated metal complex, 30 mmol of (3aS,3′aS,4S,4'S,7R,7′R,7aS,7′aS)-dodecahydro-7,7′,8,8,8′,8′-hexamethyl-3a,3′a-diphenyl-2,2′-bi-4,7-methanol-1,3,2-benzodioxaborole [916771-67-0], 45 mmol of potassium acetate [127-08-2] and 0.45 mmol of trans-dichlorobis(tricyclohexylphosphine)palladium(II) [29934-17-6] are weighed out, and 100 ml of 1,4-dioxane are added. The reaction mixture is inertized with argon and stirred under reflux for 24-48 hours. After cooling, the reaction solution is filtered through Celite, and the Celite is rinsed with 2×50 ml of 1,4-dioxane. Subsequently, the filtrate is concentrated on a rotary evaporator and the remaining residue is worked up by extraction with DCM and water. The organic phase is removed and washed with saturated sodium chloride solution. 50 ml of ethanol are then added to the organic phase, and then the dichloromethane is evaporated off on a rotary evaporator. The precipitated solids are filtered off with suction, washed twice with 10 ml each time of ethanol and then dried under reduced pressure. Subsequently, the 1:1 mixture of the diastereomers obtained is separated by means of chromatographic methods. The respective product is referred to as Ir(Lx-3boron-S) or MSx-3-boron-S. The yield reported is initially the yield of the diastereomer mixture; the separation of the diastereomers is described in detail in point 5.

(34) The following compounds can be prepared analogously to these methods:

(35) TABLE-US-00002 Reactant Variant > borylated complex Yield Ir(L2-3Br) 82% Ir(L3-3Br) 80% Ir(L1-3Br) 76% Ir(L2-Br) 72% Ir(L3-2Br) 80% 454454- 92-3 MS1 78% 873434- 28-7 MS2 85% 1651859- 63-0 MS3 82% 1803319- 99-4 MS4 0 70% 1989601- 72-0 MS5 65% 1989601- 78-6 MS6 67% 2054152- 16-6 MS7 60%
Variant 4:
Borylation of the Halogenated Complexes Via Lithiation and Subsequent Quenching with an Electrophilic Boron Compound

(36) In a 250 ml two-neck flask with magnetic stirrer bar and argon connection, 1 mmol of a tribrominated metal complex is suspended in 100 ml of absolute THF, and cooled to internal temperature of −65° C. in an acetone/dry ice bath while stirring. Then 15 mmol of a 1.7 mol/l solution of tert-butyllithium in pentane [594-19-4] are added dropwise in such a way that the internal temperature does not exceed −55° C. The mixture is stirred at −65° C. for 5 h, then the (3aS,4s,6S,7aR)-hexahydro-3a,5,5-trimethyl-2-(1-methylethoxy)-4,6-methano-1,3,2-benzodioxaborole (15 mmol) [819816-59-6] in 20 ml of absolute THF is rapidly added dropwise. The reaction mixture is allowed to warm up gradually to room temperature and stirred at room temperature overnight. Then 1 ml of MeOH is added and the mixture is concentrated on a rotary evaporator. The residue is taken up in 100 ml of DCM, washed once with 25 ml of water and once with 25 ml of saturated NaCl solution, dried over sodium sulfate and filtered through a silica gel bed. The silica gel is rinsed twice with 50 ml each time of DCM, 30 ml of ethanol are added to the filtrate, the DCM is drawn off at bath temperature 50° C. on a rotary evaporator up to 500 mbar, and the precipitated solids are filtered off with suction using a double-ended frit, washed twice with 5 ml each time of ethanol and then dried under reduced pressure. The crude product can be purified by chromatography in order to remove impurities prior to separation of the diastereomers. Subsequently, the 1:1 mixture of the diastereomers obtained is separated by means of chromatographic methods. The respective product is referred to as Ir(Lx-3boron-(+)) or MSx-3boron-(+).

(37) The following compounds can be prepared:

(38) TABLE-US-00003 Reactant Variant > borylated complex Yield Ir(L3-3Br) 54% 1651859- 63-0 MS3 50%

5. Chromatographic Separation of the Diastereomers Via Preparative HPLC Using the Example of Ir(L3-3Boron-(+))

(39) ∧-Ir(L3-3Boron-(+)) and Δ Ir(L3-3Boron-(+))

(40) First of all, an analytical HPLC-MS method is chosen to separate the two isomers and to confirm them on the basis of their molar mass. No assignment of the ∧ or Δ isomer takes place here. Therefore, the isomers are referred to hereinafter as isomer 1 (abbreviated to I1) or isomer 2 (abbreviated to I2) I1-Ir(Lx-3-boron-y) and I2-Ir(Lx-3boron-y) or I1-MSx-3boron-y and I2-MSx-3boron-y. The number of boron atoms is given by the number before the word “boron”.

(41) The analytical separation is conducted in a DIONEX Ultimate 3000 LC system; the masses are detected with a mass spectrometer with an APCI (mode: positive) ion source. Separation is accomplished using a 150 mm×4.6 mm/3 μm Purospher Star RP-18e column. A gradient program with an acetonitrile/tetrahydrofuran solvent mixture is run.

(42) FIG. 1 shows the chromatogram from the analytical separation of the isomers of Ir(L3-3boron-(+)).

(43) FIG. 2 shows the assignment of the mass peaks to the retention times of the isomers of Ir(L3-3boron-(+)).

(44) Subsequently, the analytical method is used as the starting point for the preparative separation. For the preparative separation, 2000 mg of the diastereomer mixture are divided between 30 HPLC runs. In this way, it is possible to obtain 840 mg of the isomer I1-Ir(L3-3boron-(+)) with a purity of 99.5% and 864 mg of the isomer I2-Ir(L3-3boron-(+)) with a purity of 99.6%.

(45) The following enantiomerically pure compounds can be obtained analogously to this method:

(46) TABLE-US-00004 Isomer > Amount > Purity I1-Ir(L2-3boron-(+)) > 782 mg > 99.4% I1-Ir(L1-3boron-S) > 860 mg > 99.5% I1-Ir(L2-boron-(+)) > 793 mg > 99.7% I1-Ir(L3-2boron-D) > 831 mg > 99.1% I1-MS1-3boron-D > 824 mg > 99.1% I1-MS2-3boron-S > 796 mg > 99.8% I1-MS3-3boron-(+) > 884 mg > 99.0% I1-MS4-3boron-D > 910 mg > 98.8% I1-MS5-2boron-S > 852 mg > 99.7% I1-MS6-boron-(+) > 812 mg > 99.7% I1-MS7-2boron-(+) > 450 mg > 98.1% I2-Ir(L2-3boron-(+)) > 760 mg > 99.7% I2-Ir(L1-3boron-S) > 800 mg > 99.3% I2-Ir(L2-boron-(+)) > 810 mg > 99.3% I2-Ir(L3-2boron-D) > 808 mg > 99.5% I2-MS1-3boron-D > 800 mg > 99.2% I2-MS2-3boron-S > 812 mg > 99.6% I2-MS3-3boron-(+) > 836 mg > 99.5% I2-MS4-3boron-D > 838 mg > 99.4% I2-MS5-2boron-S > 897 mg > 99.8% I2-MS6-boron-(+) > 823 mg > 99.2% I2-MS7-2boron-(+) > 601 mg > 98.8%

(47) 5 g of a mixture of I1-Ir(L2-boron-(+)) and I2-Ir(L2-boron-(+)) are separated by chromatography on an automated column system (Companion from Axel Semrau). The eluent mixture used is a gradient of dichloromethane and toluene.

(48) Column yield: I1-Ir(L2-boron-(+)) 2.1 g, purity 98.2%, and I2-Ir(L2-boron-(+)) 2.2 g, purity 98.0%. The two diastereomers I1-Ir(L2-boron-(+)) and 12-Ir(L2-boron-(+)), separately from one another, are hot-extracted three times more each with ethyl acetate and then heat-treated under high vacuum.

(49) Yield: I1-Ir(L2-boron-(+)) 1.2 g, purity 99.6%, and I2-Ir(L2-boron-(+)) 1.0 g, purity 99.5%.

6. Suzuki Coupling of the Enantiomerically Pure Borylated Complexes

(50) Variant 1: Suzuki Coupling in a Biphasic Aqueous-Organic Medium

(51) To a mixture of 1 mmol of the borylated metal complex, 6 mmol of the bromide, 12 mmol of tripotassium phosphate [7778-53-2], 30 ml of toluene, 10 ml of dioxane and 10 ml of water are added 0.12 mmol of tri-o-tolylphosphine [6163-58-2] and 0.02 mmol of palladium(II) acetate [3975-31-3], and the mixture is stirred well at 100° C. for 48 h. After cooling, the organic phase is removed, washed twice with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution and then dried over magnesium sulfate, the magnesium sulfate is filtered off, and the filtrate is concentrated to dryness. The crude product thus obtained is purified by chromatography or flash chromatography (CombiFlash Torrent from Axel Semrau).

(52) Variant 2: Suzuki Coupling in a Monophasic Dipolar Aprotic Medium

(53) To a mixture of 1 mmol of the borylated metal complex, 6 mmol of the bromide, 12 mmol of tripotassium phosphate trihydrate [22763-03-7] and 30 ml of DMSO is added 0.1 mmol of tetrakis(triphenylphosphino)palladium(0) [14221-01-3], and the mixture is stirred well at 80° C. for 48 h. After cooling, the DMSO is substantially removed under reduced pressure, the residue is taken up in 100 ml of dichloromethane and filtered through a silica gel bed in the form of a dichloromethane slurry, the bed is washed through with 50 ml of dichloromethane and then the organic phase is concentrated to dryness under reduced pressure. The further purification of the crude product thus obtained is effected as described under variant 1.

Example I1-Ir1

(54) ##STR00156##

(55) Procedure according to variant 2. Use of 1.49 g (1 mmol) of I1-Ir(L2-3boron-(+)), 1.40 g (6 mmol) of 1-bromo-3-phenylbenzene [2113-57-7], 3.20 g (12 mmol) of tripotassium phosphate trihydrate, 115 mg (0.1 mmol) of tetrakis(triphenylphosphino)palladium(0). Yield: 1.10 g (0.78 mmol), 78%. Purity: >99.8% by HPLC.

(56) In an analogous manner, it is possible to prepare the following compounds:

(57) TABLE-US-00005 Ex. Product > Reactant > Variant > Bromide Yield I2-Ir1 72% I1-Ir2 80% I2-Ir2 I1-Ir(L3-3boron-(+)) > variant 1 > bromobenzene [108-86-1] 82% I1-Ir3 58% I2-Ir3 I2-Ir(L1-3boron-S) > variant 2 > 4-bromodibenzofuran [89827-45-2] 54% I1-Ir4 0 88% I2-Ir4 I2-MS1-3boron-D − variant 1 > m-bromoquaterphenyl [1233200-57-1] 81% I1-Ir5 74% I2-Ir5 I2-MS2-3boron-S > variant 2 > 9,9-dimethyl-2-bromofluorene [28320-31-2] 79% I1-Ir6 48% I2-Ir6 I2-MS3-3boron-(+) > variant 1 > 2,6-dimethylphenyl bromide [576-22-7] 50% I1-Ir7 39% I2-Ir7 I2-MS4-3boron-D > variant 2 > bromobenzene [108-86-1] 36% I1-Ir8 65% I2-Ir8 I2-Ir(L2-boron-(+)) > variant 2 > pentadeuterobromobenzene [4165-57-5] 60% I1-Ir9 37% I2-Ir9 I2-Ir(L3-2boron-D) > variant 1 > 1-bromo-6-tert-butlybenzene [3972-64-3] 42% I1-Ir10 55% I2-Ir10 I2-MS5-2boron-S > variant 2 > 1-bromo-3,5-bis(tert-butyl)benzene [3972-64-3] 60% I1-Ir11 68% I2-Ir11 I2-MS6-boron-(+) > variant 1 > 1-bromo-3,5-bis(tert-butyl)benzene [3972-64-3] 64% I1-Ir12 41% I2-Ir12 I2-MS7-2boron-(+) > variant 1 > 9,9′-spirobi[9H-fluorene] [171408-76-7] 36%

7. Physical Properties of the Enantiomerically Pure Compounds Compared to the Racemate

(58) The enantiomerically pure compounds especially feature improved solubility and lower sublimation temperatures compared to the racemate. Of particular significance here is solubility in toluene (abbreviated hereinafter as Tol) and 3-phenoxytoluene (abbreviated hereinafter as 3-PT), since these solvents are used to construct solution-based OLEDs. For the processing of the complexes of the invention (spin-coating, inkjet printing, nozzle printing, bar coating, etc.), solutions of prolonged stability having solids contents of 5-20 mg/ml are required.

(59) Likewise of crucial significance for the construction of vacuum-processed OLEDs are low sublimation temperatures of the complexes (under high vacuum).

(60) TABLE-US-00006 Solubility at 25° C. Sublimation temperature Emitter in mg/ml at 10.sup.−5 mbar in ° C. Ir1 (racemate) 12 (Tol)/22 (3-PT) 430 I1-Ir1 18 (Tol)/35 (3-PT) 410 I2-Ir1 18 (Tol)/35 (3-PT) 410 Ir2 (racemate) 6 (Tol)/14 (3-PT) 420 I1-Ir2 16 (Tol)/26 (3-PT) 405 I2-Ir2 15 (Tol)/27 (3-PT) 405 Ir3 (racemate) 3 (Tol)/5 (3-PT) 435 I1-Ir3 9 (Tol)/14 (3-PT) 415 I2-Ir3 8 (Tol)/13 (3-PT) 420 Ir4 (racemate) 8 (Tol)/21 (3-PT) — I1-Ir4 16 (Tol)/34 (3-PT) — I2-Ir4 16 (Tol)/32 (3-PT) — Ir5 (racemate) 4 (Tol)/6 (3-PT) — I1-Ir5 10 (Tol)/14 (3-PT) — I2-Ir5 9 (Tol)/14 (3-PT) — Ir6 (racemate) 3 (Tol)/4 (3-PT) 370 I1-Ir6 10 (Tol)/14 (3-PT) 350 I2-Ir6 9 (Tol)/14 (3-PT) 355 Ir7 (racemate) 14 (Tol)/28 (3-PT) 360 I1-Ir7 23 (Tol)/40 (3-PT) 340 I2-Ir7 25 (Tol)/39 (3-PT) 340 Ir8 (racemate) 5 (Tol)/10 (3-PT) 420 I1-Ir8 8 (Tol)/14 (3-PT) 400 I2-Ir8 9 (Tol)/15 (3-PT) 400 Ir9 (racemate) 15 (Tol)/35 (3-PT) 425 I1-Ir9 15 (Tol)/40 (3-PT) 410 I2-Ir9 18 (Tol)/44 (3-PT) 410 Ir10 12 (Tol)/25 (3-PT) — I1-Ir10 15 (Tol)/32 (3-PT) — I2-Ir10 16 (Tol)/30 (3-PT) — Ir11 20 (Tol)/35 (3-PT) 405 I1-Ir11 22 (Tol)/40 (3-PT) 395 I1-Ir11 20 (Tol)/39 (3-PT) 390 Ir12 26 (Tol)/52 (3-PT) — I1-Ir12 30 (Tol)/55 (3-PT) — I2-Ir12 32 (Tol)/58 (3-PT) —

Example: Production of the OLEDs

(61) 1) Vacuum-Processed Devices:

(62) OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

(63) In the examples which follow, the results for various OLEDs are presented. Cleaned, coated glass plaques are used (cleaning in Miele laboratory glass washer, Merck Extran detergent), coated with structured ITO (indium tin oxide) of thickness 50 nm and pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator). Subsequently, they are coated within 30 minutes, for improved processing, with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180° C. for 10 min. These coated glass plaques form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of HTM doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm.

(64) First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as M3:M2:Ir1 (55%:35%:10%) mean here that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir1 in a proportion of 10%.

(65) Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 1. The materials used for production of the OLEDs are shown in Table 6.

(66) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, current efficiency (measured in cd/A) and voltage (measured at 1000 cd/m.sup.2 in V) are determined from current-voltage-brightness characteristics (IUL characteristics).

(67) In addition, power efficiency (measured in Im/W) and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

(68) For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminance has fallen from a particular starting luminance to a certain proportion. The figure LD50 means that the lifetime specified is the time at which the luminance has dropped to 50% of the starting luminance, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. According to the emission colour, different starting brightnesses were selected. The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a standard figure. The lifetime LD80 is defined as the time after which the luminance drops to 80% of the starting luminance in the course of operation with a constant current of 40 mA/cm.sup.2.

(69) 2) Use of Compounds of the Invention as Emitter Materials in Phosphorescent OLEDs One use of the compounds of the invention is as phosphorescent emitter materials in the emission layer in OLEDs. The iridium compounds according to Table 6 are used as a comparison according to the prior art. The results for the OLEDs are collated in Table 2.

(70) TABLE-US-00007 TABLE 1 Construction of the vacuum-processed OLEDs HTL2 EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness Ref-D1 HTM M1:IrPPy ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 35 nm 30 nm Ref-D2 HTM M1:IrPPy2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 35 nm 30 nm Ref-D3 HTM M1:M3:IrPPy ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 35 nm 30 nm Ref-D4 HTM M1:M3:IrPPy2 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 35 nm 30 nm D1 HTM M1:Ir2 (racemate) ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 35 nm 30 nm D1a HTM M1:I1-Ir2 ETM1 ETM1:ETM2 50 nm (80%:20%) 10 nm (50%:50%) 35 nm 30 nm D1b HTM M1:I2-Ir2 ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 30 nm 30 nm D2 HTM M1 M3:Ir2 (racemate) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D2a HTM M1:M3:I1-Ir2 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D2b HTM M1:M3:I2-Ir2 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D3 HTM M1:M3:Ir2 (racemate) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D3a HTM M1:M3:I1-Ir2 ETM1 ETM1:TM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D3b HTM M1:M3:I2-Ir2 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D4 HTM M6:Ir2 (racemate) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D4a HTM M6:I1-Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D4b HTM M6:I2-Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D5 HTM M6:Ir2 (racemate) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D5a HTM M6:I1-Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D5b HTM M6:I2-Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D6 HTM M6:Ir2 (racemate) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D6a HTM M6:I1-Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D6b HTM M6:I2-Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D7 HTM M1:M3:Ir1 (racemate) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D7a HTM M1:M3:I1-Ir1 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D7b HTM M1:M3:I2-Ir1 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D8 HTM M1:Ir6 (racemate) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D8a HTM M1:I1-Ir6 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D8b HTM M1:12-Ir6 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D9 HTM M1:M2:Ir6 (racemate) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D9a HTM M1:M2:I1-Ir6 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D9b HTM M1:M2:I2-Ir6 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D10 HTM M8:Ir2 (racemate) ETM1 ETM1:ETM2 30 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D10a HTM M8:I1-Ir2 ETM1 ETM1:ETM2 30 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D10b HTM M8:I2-Ir2 ETM1 ETM1:ETM2 30 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D11 HTM M7:M10:Ir2 ETM1 ETM1:ETM2 40 nm (racemate) 10 nm (50%:50%) (50%:30%:20%) 30 nm 30 nm D11a HTM M7:M10:I1-Ir2 ETM1 ETM1:ETM2 40 nm (50%:30%:20%) 10 nm (50%:50%) 30 nm 30 nm D11b HTM M7:M10:I2-Ir2 ETM1 ETM1:ETM2 40 nm (50%:30%:20%) 10 nm (50%:50%) 30 nm 30 nm D13 HTM M1:Ir8(racemate) ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 35 nm 30 nm D13a HTM M1:I1-Ir8 ETM1 ETM1:ETM2 50 nm (80%:20%) 10 nm (50%:50%) 35 nm 30 nm D13b HTM M1:I2-Ir8 ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 30 nm 30 nm D14 HTM M1:Ir9(racemate) ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 35 nm 30 nm D14a HTM M1:I1-Ir9 ETM1 ETM1:ETM2 50 nm (80%:20%) 10 nm (50%:50%) 35 nm 30 nm D14b HTM M1:I2-Ir9 ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 30 nm 30 nm D15 HTM M1:M3:Ir11 ETM1 ETM1:ETM2 40 nm (racemate) 10 nm (50%:50%) (60%:30%:10%) 30 nm 30 nm D15a HTM M1:M3:I1-Ir11 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D15b HTM M1:M3:I2-Ir11 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm

(71) TABLE-US-00008 TABLE 2 Data of the vacuum-processed OLEDs Ex. EQE1000 (%) U1000 (V) CIE x/y LD80 (h) Ref-D1 18.3 3.2 0.33/0.62 65 Ref-D2 17.4 3.1 0.34/0.62 180 Ref-D3 17.2 3.2 0.31/0.63 90 Ref-D4 17.8 3.0 0.32/0.63 260 D1 19.2 3.0 0.33/0.63 260 D1a 19.1 3.1 0.33/0.63 270 D1b 19.2 3.1 0.33/0.63 275 D2 20.4 3.0 0.32/0.64 250 D2a 20.3 3.1 0.32/0.63 245 D2b 20.2 3.0 0.32/0.64 250 D3 21.8 2.9 0.32/0.64 270 D3a 22.0 3.0 0.32/0.64 275 D3b 22.1 2.9 0.32/0.64 265 D4 21.6 3.0 0.33/0.64 160 D4a 21.8 3.1 0.33/0.64 165 D4b 21.7 3.0 0.33/0.64 160 D5 19.7 3.5 0.33/0.64 220 D5a 19.9 3.6 0.33/0.63 230 D5b 19.8 3.5 0.33/0.64 235 D6 20.2 3.4 0.33/0.63 280 D6a 20.3 3.3 0.33/0.63 290 D6b 20.5 3.3 0.33/0.64 265 D7 21.7 3.1 0.34/0.63 240 D7a 21.5 2.9 0.34/0.63 230 D7b 21.7 3.0 0.34/0.63 235 D8 17.8 3.0 0.34/0.64 140 D8a 17.9 3.0 0.34/0.64 150 D8b 19.2 3.1 0.32/0.64 135 D9 19.3 3.0 0.32/0.64 170 D9a 19.0 3.0 0.32/0.64 170 D9b 18.0 3.0 0.34/0.64 175 D10 20.3 3.5 0.33/0.63 240 D10a 20.2 3.6 0.33/0.63 245 D10b 20.0 3.5 0.33/0.63 230 D11 20.7 3.4 0.33/0.64 250 D11a 20.9 3.3 0.33/0.64 255 D11 b 20.7 3.3 0.33/0.64 265 D13 18.7 3.1 0.33/0.63 290 D13a 19.0 3.1 0.33/0.63 300 D13b 19.1 3.0 0.33/0.63 305 D14 20.6 3.3 0.32/0.64 170 D14a 20.7 3.4 0.32/0.64 180 D14b 20.4 3.3 0.32/0.64 185 D15 21.5 3.2 0.36/0.61 150 D15a 21.8 3.2 0.37/0.61 160 D15b 21.8 3.4 0.37/0.61 155
3) Vacuum-Processed Blue-Emitting Components

(72) In the example which follows, data of blue-emitting OLEDs are presented. Processing and characterization are as described in 2). The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in Table 8 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The lifetime LD50 is defined as the time after which the luminance drops to 50% of the starting luminance with a starting brightness of 1000 cd/m.sup.2.

(73) TABLE-US-00009 TABLE 3 Construction of the blue vacuum-processed OLEDs HTL2 EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness D12 HTM EBM1 M9:Ir7 (racemate) ETM3 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D12a HTM EBM1 M9:I1-Ir7 ETM3 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D12b HTM EBM1 M9:I2-Ir7 ETM3 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm

(74) TABLE-US-00010 TABLE 4 Data of the blue vacuum-processed OLEDs Ex. EQE1000 (%) U1000 (V) CIE x/y LD50 (h) D12 7.2 5.6 0.16/0.11 100 D12a 7.1 5.5 0.16/0.11 110 D12b 7.4 5.5 0.16/0.11 100
4) Solution-Processed Devices:
A: From Soluble Functional Materials of Low Molecular Weight

(75) The iridium complexes of the invention may also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, a 20 nm hole injection layer is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200° C. for 30 minutes. The interlayer used serves for hole transport; in this case, HL-X092 from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfil the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices of type 1a contain an emission layer composed of M4:M5:IrL (40%:45%:15%), those of type 1b contain an emission layer composed of M4:M5:IrL (20%:60%:20%), and those of type 2 contain an emission layer composed of M4:M5:IrLa:IrLb (30%:34%:30%:6%); in other words, they contain two different Ir complexes. The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 10 min. Vapour-deposited above the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapour deposition systems from Lesker or the like, typical vapour deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminium (100 nm) (high-purity metal from Aldrich) is applied by vapour deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; Table 5 summarizes the data obtained.

(76) TABLE-US-00011 TABLE 5 Results with materials processed from solution Emitter EQE (%) Voltage (V) LD50 (h) Ex. Device 1000 cd/m.sup.2 1000 cd/m.sup.2 CIE x/y 1000 cd/m.sup.2 Green and red OLEDs Sol- Ir4 (racemate) 19.8 5.2 0.36/0.61 200000 Green1 Type 1a Sol- I1-Ir4 19.6 5.1 0.36/0.62 230000 Green1a Type 1a Sol- I2-Ir4 19.9 5.0 0.36/0.61 210000 Green1b Type 1a Sol- Ir4 (racemate) 19.6 4.8 0.36/0.61 210000 Green2 Type 1b Sol- I1-Ir4 19.4 4.9 0.36/0.61 215000 Green2a Type 1b Sol- I2-Ir4 19.5 4.9 0.36/0.61 230000 Green2b Type 1b Sol-Green Ir2 (racemate) 23.0 4.5 0.34/0.62 350000 3 Type 1b Sol-Green I1-Ir2 23.3 4.4 0.34/0.62 350000 3a Type 1b Sol-Green I2-Ir2 22.9 4.5 0.34/0.62 360000 3b Type 1b Sol-Green Ir1 (racemate) 21.8 4.6 0.34/0.63 230000 4 Type 1b Sol-Green I1-Ir1 21.9 4.6 0.34/0.63 240000 4a Type 1b Sol-Green I2-Ir1 21.9 4.5 0.34/0.63 240000 4b Type 1b Sol-Red 5 Ir-5 (racemate) 13.9 4.6 0.67/0.33 200000 Type 2 Sol-Red I1-Ir-5 14.0 4.5 0.67/0.33 210000 5a Type 2 Sol-Red I2-Ir-5 14.1 4.5 0.67/0.33 190000 5b Type 2 Sol-Yellow Ir10 18.8 5.1 0.45/0.54 180000 6 (racemate) Type 1b Sol-Yellow I1-Ir10 19.2 5.2 0.45/0.54 185000 6a Type 1b Sol-Yellow I2-Ir10 19.2 5.1 0.45/0.54 180000 6b Type 1b

(77) TABLE-US-00012 TABLE 6 Structural formulae of the materials used 0 0

DESCRIPTION OF THE FIGURES

(78) FIG. 1 shows the chromatogram from the analytical separation of the isomers of Ir(L3-3boron-(+)).

(79) FIG. 2 shows the assignment of the mass peaks to the retention times of the isomers of Ir(L3-3boron-(+)).