Metal complexes
View Patent ↗The present invention relates to a compound of the formula (1), a process to prepare the compound of formula (1), a formulation containing the compound of formula (1) and an electronic device containing the compound of formula (1).
1. A compound of the formula (1),
where the following applies to the symbols used:
M is a transition metal;
A is N, P, B, C − or CR;
Y is on each occurrence, identically or differently, CR 2 , NR, O S or a single bond, where a maximum of one group Y stands for a single bond;
Z is on each occurrence, identically or differently, C or N, with the proviso that both Z stand for C if Ar 3 stands for an aromatic or heteroaromatic six-membered ring, and that either both Z stand for C or one Z stands for C and the other Z stands for N if Ar 3 stands for a heteroaromatic five-membered ring;
D is on each occurrence, identically or differently, C or N;
Ar 1 is on each occurrence, identically or differently, together with the group D and the three carbon atoms explicitly drawn in, one carbon bonded to Y, one carbon bonded to A and one carbon bonded to Ar 2 , an aryl or heteroaryl group having 5 to 13 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
Ar 2 is on each occurrence, identically or differently, together with the group D and the carbon atom explicitly drawn in, and bonded to Ar 1 , an aryl or heteroaryl group having 5 to 13 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
Ar 3 is, together with the two groups Z and the carbon atom, an aryl or heteroaryl group having 5 to 10 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
R and R 1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 2 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 2 ) 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 is optionally substituted by one or more radicals R 2 , where one or more non-adjacent CH 2 groups is optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , C═O, NR 2 , O, S or CONR 2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or hetero-aromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is 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, which is optionally substituted by one or more radicals R 2 ; two adjacent radicals R or two adjacent radicals R 1 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; furthermore, the radicals R 1 which are bonded to adjacent groups Ar 1 and Ar 2 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
R 2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 3 ) 2 , CN, NO 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , OSO 2 R 3 , 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 is optionally substituted by one or more radicals R 3 , where one or more non-adjacent CH 2 groups is optionally replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , C═O, NR 3 , O, S or CONR 3 and where one or more H atoms is 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 may in each case be substituted by one or more radicals R 3 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 ;
R 3 is on each occurrence, identically or differently, H, D, F or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R 3 here may also form a mono- or polycyclic, aliphatic ring system with one another.
2. The compound according to claim 1 , wherein M is selected from the group consisting of platinum, palladium, nickel, rhodium, iridium and gold.
3. The compound according to claim 1 , wherein two groups D stand for N and the other two groups D stand for C.
4. The compound according to claim 1 , wherein Y stands, identically or differently on each occurrence, for CR 2 or for a single bond, where a maximum of one group Y stands for a single bond.
5. The compound according to claim 1 , wherein the two bridges Y are selected identically.
6. A compound according to claim 1 of the formula (2),
where the symbols used have the meanings given in claim 1 .
7. The compound according to claim 1 , wherein Ar 3 is selected from the structures of the formulae (3), (4) and (5),
where X stands, identically or differently on each occurrence, for CR 1 or N or where two adjacent groups X in formula (3) together stand for NR, O or S and the other group X stands for CR 1 or N; * indicates the bond to Y, and # indicates the bond to A.
8. The compound according to claim 1 , wherein Ar 1 is selected, identically or differently on each occurrence, from the structures of the formulae (6) to (9), (11) and (14),
where the bond to A, Y, M and Ar 2 is in each case indicated by the dashed bonds, X stands on each occurrence, identically or differently, for CR 1 or N, V stands on each occurrence, identically or differently, for O, S or NR 1 and R 1 has the same meaning as described in claim 1 .
9. The compound according to claim 1 , wherein Ar 2 is selected, identically or differently on each occurrence, from the structures of the formulae (17)-(24), (27)-(33) and (35)-(38),
where the bond to M and Ar 1 is in each case indicated by the dashed bonds, X stands on each occurrence, identically or differently, for CR 1 or N, V stands on each occurrence, identically or differently, for O, S or NR 1 and R 1 has the same meaning as described in claim 1 .
10. The compound according to claim 1 , wherein R 1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Br, I, N(R 2 ) 2 , CN, Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more H atoms is optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 ; two adjacent radicals R 1 or two radicals R 1 on adjacent groups Ar 1 and Ar 2 here may also form a mono- or polycyclic, aliphatic ring system with one another.
11. The compound according to claim 1 , wherein, if Y stands for NR, R stands, identically or differently on each occurrence, for an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , and in that, if Y stands for CR 2 , R stands, identically or differently on each occurrence, for H, D, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more H atoms is optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 ; two or more radicals R which are bonded to the same carbon atom here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another.
12. A process for the preparation of the compound according to claim 1 which comprises reacting the free ligand with a metal compound.
13. A formulation comprising:
a) at least one compound according to claim 1 and at least one solvent, or
b) a mixture comprising at least one compound according to claim 1 and at least one further compound.
14. The formulation as claimed in claim 13 , wherein the formulation is a solution, a suspension or a mini-emulsion.
15. An electronic device which comprises the compound according to claim 1 .
16. The electronic device as claimed in claim 15 , wherein the device is an organic electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell or an organic laser diode.
17. An organic electroluminescent device which comprises the compound according to claim 1 employed as emitting compound in one or more emitting layers.
18. An organic electroluminescent device which comprises the compound according to claim 1 employed as emitting compound in one or more emitting layers in combination with one or more matrix materials.
19. The compound according to claim 1 , wherein
M is selected from the group consisting of Pt(II), Pd(II), Ni(II), Rh(I), Ir(I) and Au(III);
D is on each occurrence, identically or differently, C or N, where two groups D stand for N and the other two groups D stand for C;
Ar 3 is selected from the structures of the formulae (3), (4) or (5)
where X stands, identically or differently on each occurrence, for CR 1 or N or where two adjacent groups X in formula (3) together stand for NR, O or S and the other group X stands for CR 1 or N; * indicates the bond to Y, and # indicates the bond to A;
Ar 1 is selected from the structures of the formulae (6) to (9), (11) and (14),
where the bond to A, Y, M and Ar 2 is in each case indicated by the dashed bonds, X stands on each occurrence, identically or differently, for CR 1 or N, V stands on each occurrence, identically or differently, for O, S or NR 1 ;
Ar 2 is selected from the structures of the formulae (17) to (24), (27)-(33) and (35)-(38)
where the bond to M and Ar 1 is in each case indicated by the dashed bonds, X stands on each occurrence, identically or differently, for CR 1 or N, V stands on each occurrence, identically or differently, for O, S or NR 1 ;
R 1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Br, I, N(R 2 ) 2 , CN, Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more H atoms is optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 ; two adjacent radicals R 1 or two radicals R 1 on adjacent groups Ar 1 and Ar 2 here may also form a mono- or polycyclic, aliphatic ring system with one another;
R is, for Y═NR, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 ; and is, for Y═CR 2 , identically or differently, H, D, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more H atoms is optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 ; or two or more radicals R which are bonded to the same carbon atom here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another.
20. The compound according to claim 1 , wherein M=Pt and A=N.