Metal complexes having azaborol ligands and electronic device having the same

1. An electronic device comprising a compound of formula (I)

M(L) n (L′) m (L″) o   (I)

where said compound of formula (I) comprises a moiety M(L) n of formula (II) and/or (III) and/or (IV):

wherein

M is a metal;

Y is on each occurrence, in each case independently of one another, NR 3 , O or S;

X is on each occurrence, in each case independently of one another, CR 1 or N;

R 1 is on each occurrence, in each case independently of one another, H, D, F, Cl, Br, I, CHO, N(R 2 ) 2 , N(Ar) 2 , C(═O)Ar, P(═O)(Ar) 2 , S(═O)Ar, S(═O) 2 Ar, CR 2 ═C(R 2 ) 2 , CR 2 ═CR 2 Ar, CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , B(R 2 ) 2 , B(N(R 2 ) 2 ) 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which are 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 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , 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, which in each case are optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems, and wherein two or more adjacent substituents R 1 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

R 2 is on each occurrence, in each case independently of one another, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, 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 or aromatic ring system with one another;

R 3 is on each occurrence, in each case independently of one another, H, D, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ; or R 3 is a coordinating group, wherein R 3 bonds to the metal M via a charged or uncharged exocyclic or endocyclic donor atom D;

a plurality of part-ligands L here may form a polydentate or polypodal ligand with one another or L together with L′ and/or L″, optionally via a link via R 3 ;

Ar is on each occurrence, in each case independently of one another, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R 1 ;

L′ and L″

are any desired co-ligands; and

wherein

n is 1, 2, 3, 4, 5, or 6, o is 0, 1, 2, 3, 4, or 5, and m is 0, 1, 2, 3, 4, or 5, if M has the coordination number 6,

n is 1, 2, 3, 4, or 5, o is 0, 1, 2, 3, or 4 and m is 0, 1, 2, 3, or 4, if M has the coordination number 5, and

n is 1, 2, 3, or 4, m is 0, 1, 2, or 3, and o is 0, 1, 2, or 3, if M has the coordination number 4.

2. The electronic device of claim 1 , wherein said device is selected from the group consisting of organic electroluminescent devices, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic integrated circuits, organic solar cells, organic field-quench devices, light-emitting electrochemical cells, organic photoreceptors and organic laser diodes.

3. The electronic device of claim 1 , wherein moiety M(L) n of formula (II), (III), and/or (IV) conforms to formula (IIa), (IIIa), (IVa), (IIb), (IIIb), or (IVb):

wherein

D 1 is on each occurrence, in each case independently of one another, an endocyclic donor atom selected from the group consisting of B, C, N, O and S;

D 2 is on each occurrence, in each case independently of one another, an exocyclic donor group selected from the group consisting of O, S, NR 1 , N(R 1 ) 2 , PR 1 , P(R 1 ) 2 , P(O)R 1 , P(O)(R 1 ) 2 , AsR 1 , As(R 1 ) 2 , As(O)R 1 , As(O)(R 1 ) 2 , SbR 1 , Sb(R 1 ) 2 , Sb(O)R 1 , Sb(O)(R 1 ) 2 , BiR 1 , Bi(R 1 ) 2 , Bi(O)R 1 , Bi(O)(R 1 ) 2 , OR 1 , SR 1 , SeR 1 and TeR 1 ;

X 1 is on each occurrence, in each case independently of one another, C or N;

Cy1 is an aromatic or heteroaromatic group or an aromatic or heteroaromatic ring system having 5 to 30 ring atoms, where X 1 and D 1 are present in the aromatic or heteroaromatic group or the aromatic or heteroaromatic ring system, and D 2 is bonded as an exocyclic donor atom or exocyclic donor group.

4. The electronic device of claim 1 , wherein D 1 is on each occurrence, in each case independently of one another, N, O or S, and D 2 is on each occurrence, in each case independently of one another, O, S, NR 1 , N(R 1 ) 2 , PR 1 , or P(R 1 ) 2 .

5. The electronic device of claim 1 , wherein Y is NR 3 .

6. The electronic device of claim 1 , wherein R 3 in formula II, III or IV or Cy 1 in the formulae IIa, IIIa, IVa, IIb, IIIb, and IVb is selected from structures (1) to (24):

wherein

X is on each occurrence, in each case independently of one another, CR 1 or N, the dashed line denotes a bond to the nitrogen atom of the boron/nitrogen heterocycle, and

* indicates the position at which the group coordinates to the metal.

7. The electronic device of claim 1 , wherein the moiety M(L) n is selected from formulae (IIc), (IIIc), and/or (IVc):

wherein

Z is any desired bridging unit.

8. The electronic device of claim 1 , wherein the compound of formula (I) comprises only ligands L or wherein the compound of formula (I) is hexacoordinated and comprises two or three bidentate ligands L or two tridentate ligands L or wherein the compound of formula (I) is coordinated in a square-planar or tetrahedral manner and comprises one or two bidentate ligands L or one tetradentate ligand L.

9. A compound of formula (I)

M(L) n (L′) m (L″) o   (I)

wherein said compound of formula (I) comprises a moiety M(L) n of formula (II), (III) and/or (IV):

wherein

M is a metal;

Y is on each occurrence, in each case independently of one another, NR 2 , O or S;

X is on each occurrence, in each case independently of one another, CR 1 or N;

R 1 is on each occurrence, in each case independently of one another, H, D, F, Cl, Br, I, CHO, N(Ar) 2 , C(═O)Ar, P(═O)(Ar) 2 , S(═O)Ar, S(═O) 2 Ar, CR 2 ═C(R 2 ) 2 , CR 2 ═CR 2 Ar, CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , B(R 2 ) 2 , B(N(R 2 ) 2 ) 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is 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 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , 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, which in each case is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems, wherein two or more adjacent substituents R 1 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

R 2 is on each occurrence, in each case independently of one another, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, 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 or aromatic ring system with one another;

R 3 is on each occurrence, in each case independently of one another, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ; at least one radical R 3 here is a coordinating group which bonds to the metal M via a charged or uncharged exocyclic or endocyclic donor atom D;

a plurality of part-ligands L here may form a polydentate or polypodal ligand with one another or L together with L′ and/or L″, optionally via a link via R 3 ;

Ar is on each occurrence, in each case independently of one another, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R 1 ; and

L′ and L″

are any desired co-ligands; and

wherein

n is 1, 2, 3, 4, 5, or 6, o is 0, 1, 2, 3, 4, or 5, and m is 0, 1, 2, 3, 4, or 5, if M has the coordination number 6,

n is 1, 2, 3, 4, or 5, o is 0, 1, 2, 3, or 4 and m is 0, 1, 2, 3, or 4, if M has the coordination number 5, and

n is 1, 2, 3, or 4, m is 0, 1, 2, or 3, and o is 0, 1, 2, or 3, if M has the coordination number 4.

10. The compound of claim 9 , wherein the moiety M(L) n conforms to formula (IIa), (IIIa), (IVa), (IIb), (IIIb), or (IVb):

D 1 is on each occurrence, in each case independently of one another, an endocyclic donor atom selected from the group consisting of B, C, N, O, and S;

D 2 is on each occurrence, in each case independently of one another, an exocyclic donor group selected from the group consisting of O, S, NR 1 , N(R 1 ) 2 , PR 1 , P(R 1 ) 2 , P(O)R 1 , P(O)(R 1 ) 2 , AsR 1 , As(R 1 ) 2 , As(O)R 1 , As(O)(R 1 ) 2 , SbR 1 , Sb(R 1 ) 2 , Sb(O)R 1 , Sb(O)(R 1 ) 2 , BiR 1 , Bi(R 1 ) 2 , Bi(O)R 1 , Bi(O)(R 1 ) 2 , OR 1 , SR 1 , SeR 1 , and TeR 1 ;

X 1 is on each occurrence, in each case independently of one another, C or N;

Cy1 is an aromatic or heteroaromatic group or an aromatic or heteroaromatic ring system having 5 to 30 ring atoms, where X 1 and D 1 are present in the aromatic or heteroaromatic group or the aromatic or heteroaromatic ring system, and D 2 is bonded as an exocyclic donor atom or exocyclic donor group.

11. The compound of claim 9 , wherein R 3 or Cy1 is selected from structures (1) to (24):

wherein

X is on each occurrence, in each case independently of one another, CR 1 or N, the dashed line denotes a bond to the nitrogen atom of the boron/nitrogen heterocycle, and

* indicates the position at which the group coordinates to the metal.

12. The compound of claim 9 , wherein the moiety M(L) n is selected from formulae (Iic), (IIIc), and (IVc):

wherein

Z is any desired bridging unit.

13. The electronic device of claim 1 , wherein said compound of formula (I) is an emitter compound, a matrix material, a hole-blocking material, and/or an electron-transport material.

14. A compound of formula (V), (VI), or (VII):

wherein

Y is on each occurrence, in each case independently of one another, NR 2 , O or S;

X is on each occurrence, in each case independently of one another, CR 1 or N;

R 1 is on each occurrence, in each case independently of one another, H, D, F, Cl, Br, I, CHO, N(Ar) 2 , C(═O)Ar, P(═O)(Ar) 2 , S(═O)Ar, S(═O) 2 Ar, CR 2 ═C(R 2 ) 2 , CR 2 ═CR 2 Ar, CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , B(R 2 ) 2 , B(N(R 2 ) 2 ) 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is 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 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , 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, which in each case is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems, wherein two or more adjacent substituents R 1 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

R 2 is on each occurrence, in each case independently of one another, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, 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 or aromatic ring system with one another;

R 3 is selected from structures (1) to (24):

wherein

X is on each occurrence, in each case independently of one another, CR 1 or N, the dashed line denotes a bond to the nitrogen atom of the boron/nitrogen heterocycle, and

* indicates the position at which the group coordinates to the metal;

Ar is on each occurrence, in each case independently of one another, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R 1 ; and

R 4 is H or halogen;

with the proviso that the following compounds are excluded:

15. A process for preparing the compound of claim 9 comprising reacting a compound of formula (V), (VI), or (VII):

wherein

Y is on each occurrence, in each case independently of one another, NR 2 , O or S;

X is on each occurrence, in each case independently of one another, CR 1 or N;

R 1 is on each occurrence, in each case independently of one another, H, D, F, Cl, Br, I, CHO, N(Ar) 2 , C(═O)Ar, P(═O)(Ar) 2 , S(═O)Ar, S(═O) 2 Ar, CR 2 ═C(R 2 ) 2 , CR 2 ═CR 2 Ar, CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , B(R 2 ) 2 , B(N(R 2 ) 2 ) 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is 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 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , 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, which in each case is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems, wherein two or more adjacent substituents R 1 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

R 2 is on each occurrence, in each case independently of one another, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, 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 or aromatic ring system with one another;

R 3 is selected from structures (1) to (24):

wherein

X is on each occurrence, in each case independently of one another, CR 1 or N,

the dashed line denotes a bond to the nitrogen atom of the boron/nitrogen heterocycle, and

* indicates the position at which the group coordinates to the metal;

Ar is on each occurrence, in each case independently of one another, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R 1 ; and

R 4 is H or halogen;

with the proviso that the following compounds are excluded:

with a metal alkoxide of formula (47), a metal ketoketonate of formula (48) or a metal halide of formula (49):

wherein

M is a metal;

R 2 is on each occurrence, in each case independently of one another, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, 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 or aromatic ring system with one another;

Hal is on each occurrence, identically or differently, F, Cl, Br or I;

Lig is on each occurrence, identically or differently, a neutral or monoanionic, monodentate or bidentate ligand;

q is on each occurrence, identically or differently, 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

r is on each occurrence, identically or differently, 1, 2, 3, 4 or 5;

wherein the metal ketoketonate of formula (48) and the metal halide of formula (49) is optionally charged and comprises one or more counterions; and

wherein the metal alkoxide of formula (47), the metal ketoketonate of formula (48), and the metal halide of formula (49) are optionally in the form of the hydrate.