Metal complexes

1. A compound of formula (1)

M(L) n (L′) m   (1)

comprising a moiety M(L) n of formulae (2), (3), or (4):

wherein:

M is a transition metal;

X is selected, on each occurrence, identically or differently, from the group consisting of CR and N;

R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 1 ) 2 , CN, NO 2 , OH, COOH, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 C atoms, each of which are optionally substituted by one or more radicals R 1 , and wherein one or more non-adjacent CH 2 groups are optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, NR 1 , O, S, or CONR 1 , and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R 1 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R 1 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R 1 , or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R 1 ; and wherein two adjacent radicals R optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another;

R 1 is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 C atoms, each of which are optionally substituted by one or more radicals R 2 , and wherein one or more non-adjacent CH 2 groups are optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , C═O, NR 2 , O, S, or CONR 2 , and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R 2 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R 2 , or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R 2 ; and wherein two or more adjacent radicals R 1 with one another or R 1 with R optionally define a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;

R 2 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic, and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F; and wherein two or more substituents R 2 optionally define a mono- or polycyclic, aliphatic ring system with one another;

L′ is, identically or differently on each occurrence, any desired co-ligand;

n is 1, 2, or 3;

m is 0, 1, 2, 3, or 4;

wherein

a plurality of ligands L are optionally linked to one another or L is optionally linked to L′ via a single bond or a divalent or trivalent bridge and thus form a tridentate, tetradentate, pentadentate, or hexadentate ligand system;

a substituent R optionally additionally coordinates to the metal; and

two adjacent groups X are CR and the respective radicals R, together with the C atoms, form a ring of formula (5) or (6);

wherein

R 1 and R 2 are as defined above;

the dashed bonds indicate the linking of the two carbon atoms in the ligand;

A 1 and A 3

are, identically or differently, on each occurrence, C(R 3 ) 2 , O, S, NR 3 , or C(═O);

A 2 is C(R 1 ) 2 , O, S, NR 3 , or C(═O);

G is an alkylene group having 1, 2, or 3 C atoms optionally substituted by one or more radicals R 2 , or is —CR 2 ═CR 2 — or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms optionally substituted by one or more radicals R 2 ; and

R 3 is, identically or differently on each occurrence, F, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms optionally substituted by one or more radicals R 2 , wherein one or more non-adjacent CH 2 groups are optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , C═O, NR 2 , O, S, or CONR 2 and wherein one or more H atoms are optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R 2 , or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R 2 ; and wherein two radicals R 3 bonded to the same carbon atom optionally define an aliphatic or aromatic ring system with one another and thus form a spiro system; and wherein R 3 optionally defines an aliphatic ring system with an adjacent radical R or R 1 ; and

with the proviso that two heteroatoms are not bonded directly to one another in A 1 -A 2 -A 3 .

2. The compound of claim 1 , wherein M is selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold.

3. The compound of claim 1 , wherein M is selected from the group consisting of molybdenum, tungsten, rhenium, ruthenium, osmium, iridium, copper, platinum, and gold.

4. The compound of claim 1 , wherein the moiety of formula (2) is selected from the group consisting of formulae (2-A) to (2-Q), the moiety of formula (3) is selected from the group consisting of formulae (3-A) to (3-F), the moiety of formula (4) is selected from the group consisting of formulae (4-A) to (4-F):

5. The compound of claim 1 , wherein the moiety of formula (2) is selected from the group consisting of formulae (2-1) to (2-5), the moiety of formula (3) is selected from the group consisting of formulae (3-1) to (3-3), and the moiety of formula (4) is selected from the group consisting of formulae (4-1) to (4-4):

wherein

* in each case denotes the positions which are CR, wherein the respective radicals R, together with the C atoms to which they are bonded, define a ring of formula (5) or (6).

6. The compound of claim 1 , wherein the structure of formula (5) is selected from the group consisting of formulae (5-A), (5-B), (5-C), and (5-D) and the structure of formula (6) is selected from the group consisting of formulae (6-A), (6-B), and (6-C):

wherein

A 1 , A 2 , and A 3 are, identically or differently on each occurrence, O or NR 3 .

7. The compound of claim 1 , wherein G is an ethylene group optionally substituted by one or more radicals R 2 .

8. The compound of claim 7 , wherein R 2 is, identically or differently on each occurrence, an alkyl group having 1 to 4 C atoms or an ortho-arylene group having 6 to 10 C atoms optionally substituted by one or more radicals R 2 .

9. The compound of claim 1 , wherein, if one or more groups X is nitrogen, a group R selected from the group consisting of CF 3 , OCF 3 , an alkyl or alkoxy group having 1 to 10 C atoms, an aromatic ring system, a heteroaromatic ring system, an aralkyl group, and a heteroaralkyl group, is bonded as a substituent adjacent to said nitrogen, or R defines a ring of formulae (5) or (6) with an adjacent group R.

10. The compound of claim 1 , wherein R, which is bonded in the ortho-position to the metal coordination, is a group selected from the group consisting of aryl groups heteroaryl groups, aryl cyanides, alkyl cyanides, aryl isocyanides, alkyl isocyanides, amines, amides, alcohols, alcoholates, thioalcohols, thioalcoholates, phosphines, phosphites, carbonyl functions, carboxylates, carbamides, or arylacetylides, and alkylacetylides, which are likewise coordinated to the metal M.

11. The compound of claim 1 , wherein said compound is selected from the structures of formulae (13) to (18):

wherein

V is a single bond, a bridging unit containing 1 to 80 atoms from the third, fourth, fifth, and/or sixth main group (i.e., group 13, 14, 15, or 16 in accordance with IUPAC), or a 3- to 6-membered homo- or heterocycle and the part-ligands L are covalently bonded to one another or L is covalently bonded to L′.

12. The compound of claim 1 , wherein L′ is selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, F − , Cl − , Br − , I − , alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic alcoholates, aromatic alcoholates, aliphatic thioalcoholates, aromatic thioalcoholates, amides, carboxylates, aryl groups, O 2− , S 2− , carbides which result in coordination in the form R—C≡M, nitrenes which result in coordination in the form R—N=M, where R generally stands for a substituent, N 3− , diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates, dithiolates, 3-(2-pyridyl)diazoles, 3-(2-pyridyl)triazoles, borates of nitrogen-containing heterocycles and bidentate monoanionic ligands L′, bidentate neutral ligands L′ and bidentate dianionic ligands L′ which, with the metal, define a cyclometallated five-membered ring or six-membered ring having at least one metal-carbon bond.

13. A process for preparing a compound of claim 1 comprising reacting a corresponding free ligand with a metal alkoxide of formula (71), a metal ketoketonate of formula (72), a metal halide of formula (73), a dimeric metal complex of formula (74), or a metal complex of formula (75):

wherein

Hal is F, Cl, Br or I,

L″ is an alcohol or a nitrile, and

(anion) is a non-coordinating anion,

and wherein metal compounds which carry both alcoholate and/or halide and/or hydroxyl and also ketoketonate radicals are optionally employed.

14. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1 , wherein one or more bonds are present from said one or more compounds to said polymer, oligomer, or dendrimer.

15. A formulation comprising an oligomer, polymer, or dendrimer of claim 14 and at least one further compound.

16. An electronic device comprising one or more oligomers, polymers, or dendrimers of claim 14 .

17. The electronic device of claim 16 , wherein said 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, and organic laser diodes.

18. The electronic device of claim 17 , comprising an emitting layer comprising a matrix material selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives, bridged carbazole derivatives, and mixtures thereof.

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

20. An electronic device comprising one or more compounds of claim 1 .

21. The electronic device of claim 20 , wherein said 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, and organic laser diodes.

22. The electronic device of claim 21 , comprising an emitting layer comprising a matrix material selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives, bridged carbazole derivatives, and mixtures thereof.

23. An organic electroluminescent device comprising a compound of claim 1 employed as an emitting compound in one or more emitting layers.