Electroluminescent bridged metal complexes for use in electronic devices

1. A compound of formula (1):

M(L) n (L′) m   (1)

comprising a substructure M(L) n of formula (2):

wherein

M is iridium or platinum;

CyC is a structure of formula (CyC-1):

wherein CyC-1 binds to CyN at the position identified by # and coordinates to M at the position identified by * and the bicyclic group containing Y and Z is bonded at the position identified by o;

CyN is a structure of formula (CyN):

wherein the CyN binds to CyC at the position identified by # and coordinates to M at the position identified by * and the bicyclic group containing Y and Z is bonded at the position identified by o;

X is the same or different in each instance and is CR or N, with the proviso that not more than two X in CyC and not more than two X in CyN are N;

Y is the same or different in each instance and is CR 2 ;

Z is the same or different in each instance and is CR 2 ;

R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 1 ) 2 , CN, NO 2 , OH, COOR 1 , C(═O)N(R 1 ) 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R′, P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 1 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, 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, each of which is optionally substituted by one or more R 1 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 1 C═CR 1 , R 1 C═N, Si(R 1 ) 2 , C═O, NR 1 , O, S, or CONR 1 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, 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 1 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 1 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 1 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 1 radicals; and wherein two adjacent R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system;

R 1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 2 ) 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, 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, each of which is optionally substituted by one or more R 2 radicals, wherein one or more nonadjacent CH 2 groups is optionally replaced by R 2 C═CR 2 , R 2 C═N, Si(R 2 ) 2 , C═O, NR 2 , O, S, or CONR 2 and wherein one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO 2 , 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 2 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 2 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 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 2 radicals; and wherein two or more adjacent R 1 radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system;

R 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 2 substituents together optionally define a mono- or polycyclic ring system;

L′ is the same or different in each instance and is a ligand;

y is in each instance 3;

z is in each instance 3;

n is 1, 2, or 3;

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′ by a single bond or a bivalent or trivalent bridge so as to form a tridentate, tetradentate, pentadentate, or hexadentate ligand system; and

R optionally is coordinated to M.

2. The compound of claim 1 , wherein CyN is selected from the group consisting of structures of formulae (CyN-1) through (CyN-4):

3. The compound of claim 1 , wherein CyC is selected from the group consisting of structures of formulae (CyC-1a) through (CyC-1k) and CyN is selected from the group consisting of structures of formulae (CyN-1a) through (CyN-1c) and (CyN-2a)

wherein R and R 1 do not form an aromatic or heteroaromatic ring system with one another and W is the same or different in each instance and is NR 1 , O, or S.

4. The compound of claim 1 , wherein the structure of formula (2) is a structure of formula (2a):

5. The compound of claim 1 , wherein R, which, when X is CR, is bonded to the corresponding carbon atom, is the same or different in each instance and is selected from the group consisting of H, D, F, Br, I, N(R 1 ) 2 , CN, Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , a straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which is optionally substituted by one or more R 1 radicals, and wherein one or more hydrogen atoms are optionally replaced by D or F, 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 1 radicals; and wherein two R radicals together or an R radical together with an R 1 radical optionally define a ring system and

wherein R, which, when Y and/or Z is CR 2 , is bonded to the corresponding carbon atom, is the same or different in each instance and is selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 10 carbon atoms and is optionally substituted by one or more R 1 radicals, a branched or cyclic alkyl group having 3 to 10 carbon atoms and is optionally substituted by one or more R 1 radicals, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms and is optionally substituted in each case by one or more R 1 radicals; and wherein two or more R radicals together optionally define a ring system.

6. The compound of claim 1 , wherein L′ is a bidentate monoanionic ligand.

7. The compound of claim 6 , wherein L′ is selected from the group consisting of 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-keto esters, carboxylates derived from aminocarboxylic acids, and ligands which have, with M, a cyclometallated five-membered ring or six-membered ring having at least one metal-carbon bond.

8. A process for preparing a compound of claim 1 comprising reacting a free ligands L and optionally L′ with a metal alkoxide of formula (58), a metal ketoketonate of formula (59), a metal halide of formula (60), a dimeric metal complex of formula (61), a metal complex of formula (62), or a metal compound bearing both alkoxide and/or halide and/or hydroxyl radicals and ketoketonate radicals:

wherein

Hal is F, Cl, Br or I;

L″ is an alcohol or a nitrile; and

(Anion)

is a non-coordinating anion.

9. An oligomer, polymer, or dendrimer comprising a compound of claim 1 , wherein one or more bonds of the compound to the polymer, oligomer, or dendrimer are present.

10. A formulation comprising a compound of claim 1 and at least one further compound.

11. A formulation comprising an oligomer, polymer or dendrimer of claim 9 and at least one further compound.

12. A compound of formula (63′)

wherein

X is the same or different in each instance and is CR or N, with the proviso that not more than two X are N;

Y is the same or different in each instance and is CR 2 ;

Z is the same or different in each instance and is CR 2 ;

y is in each instance 3; and

z is in each instance 3;

R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 1 ) 2 , CN, NO 2 , OH, COOR 1 , C(═O)N(R 1 ) 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 1 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, 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, each of which is optionally substituted by one or more R 1 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 1 C═CR 1 , R 1 C═N, Si(R 1 ) 2 , C═O, NR 1 , O, S, or CONR 1 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, 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 1 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 1 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 1 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 1 radicals; and wherein two adjacent R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system;

R 1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 2 ) 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 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, each of which may be substituted by one or more R 2 radicals, where one or more nonadjacent CH 2 groups may be replaced by R 2 C═CR 2 , R 2 C═N, Si(R 2 ) 2 , C═O, NR 2 , O, S or CONR 2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R 2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 2 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R 2 radicals; at the same time, two or more adjacent R 1 radicals together may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;

R 2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; at the same time, two or more R 2 substituents together may also form a mono- or polycyclic ring system.

13. An electronic device comprising a compound of claim 1 .

14. The electronic device of claim 13 , wherein the electronic device is an organic electroluminescent device comprising one or more emitting layers, wherein the compound is present in the one or more emitting layers as an emitting compound.

15. An electronic device comprising an oligomer, polymer, or dendrimer of claim 9 .

16. The electronic device of claim 15 , wherein the electronic device is an organic electroluminescent device comprising one or more emitting layers, wherein the oligomer, polymer, or dendrimer is present in the one or more emitting layers as an emitting compound.