Metal complexes
The present invention relates to metal complexes and to electronic devices, in particular organic electroluminescent devices, comprising these metal complexes.
1. A compound of the formula (1),
[M(L) n (L′) m ] w x+/x− [A] y z−/z+ formula (1)
where the compound of the general formula (1) contains a moiety M(L) n of the formula (2):
where the following applies to the symbols and indices used:
M is a transition metal;
Q is on each occurrence, identically or differently, N;
X is on each occurrence, identically or differently, CR or N;
Y is on each occurrence, identically or differently, a substituted or unsubstituted diatomic bridge containing, as bridge atoms, two atoms selected, identically or differently on each occurrence, from the group consisting of C, N, O, S, Si or P;
W is on each occurrence, identically or differently, CR═CR or CR═N;
Z is C;
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 is optionally substituted by one or more radicals R 1 , where one or more non-adjacent CH 2 groups is optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, NR 1 , O, S or CONR 1 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case be substituted by one or more radicals R 1 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is 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, which is optionally substituted by one or more radicals R 1 ; two adjacent radicals R here may also form 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 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, 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 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 or more adjacent radicals R 2 here may form a mono- or polycyclic, aliphatic ring system with one another;
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, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R 2 here may also form a mono- or polycyclic, aliphatic ring system with one another;
L′ is, identically or differently on each occurrence, any desired co-ligand;
A is a counterion;
n is 1, 2 or 3;
m is 0, 1, 2, 3 or 4;
w is 1, 2 or 3;
x, y, z are on each occurrence, identically or differently, 0, 1, 2 or 3; where (w·x)=(y·z);
a plurality of ligands L here may also be linked to one another or L is optionally linked to L′ via any desired bridge V and thus form a tridentate, tetradentate, pentadentate or hexadentate ligand system;
furthermore, a substituent R may also additionally be coordinated to the metal.
2. The compound according to 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 according to claim 1 , wherein one of the two bridge atoms in the group Y represents a carbon atom and in that the other bridge atom is selected from C, N or O, where the atoms may in each case be substituted by radicals R.
4. The compound according to claim 1 , wherein the bridge Y is selected from the structures —CR═CR—, —CR═N—, —C(═O)—CR 2 —, —C(═O)—NR—, —C(═O)—O— or —CR 2 —CR 2 — or from the structures of the formulae (A) to (E),
where R has the meaning given in claim 1 and the dashed bonds in each case indicate the bonding of this group in the corresponding ligand.
5. The compound according to claim 1 , wherein X stands for CR or CH.
6. A compound of the formula (1),
[M(L) n (L′) m ] w x+/x− [A] y z−/z+ formula (1)
where the compound of the general formula (1) contains a moiety M(L) n of the formula (2):
where the following applies to the symbols and indices used:
M is a transition metal;
Q is on each occurrence, identically or differently, N;
X is on each occurrence, identically or differently, CR or N;
Y is on each occurrence, identically or differently, a substituted or unsubstituted diatomic bridge containing, as bridge atoms, two atoms selected, identically or differently on each occurrence, from the group consisting of C, N, O, S, Si or P;
W is on each occurrence, identically or differently, CR, N, CR═CR or CR═N if Q stands for N, with the proviso that W stands for CR═CR or CR═N if Y stands for CR═CR or for CR═N;
or W is NR if Q stands for C;
Z is C if W in this ligand stands for CR═CR or CR═N; or one Z stands for C and the other Z stands for N if W in this ligand stands for CR or N or NR;
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 is optionally substituted by one or more radicals R 1 , where one or more non-adjacent CH 2 groups is optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, NR 1 , O, S or CONR 1 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case be substituted by one or more radicals R 1 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is 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, which is optionally substituted by one or more radicals R 1 ; two adjacent radicals R here may also form 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)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, 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 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 or more adjacent radicals R 2 here may form a mono- or polycyclic, aliphatic ring system with one another;
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, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R 2 here may also form a mono- or polycyclic, aliphatic ring system with one another;
L′ is, identically or differently on each occurrence, any desired co-ligand;
A is a counterion;
n is 1, 2 or 3;
m is 0, 1, 2, 3 or 4;
w is 1, 2 or 3;
x, y, z are on each occurrence, identically or differently, 0, 1, 2 or 3; where (w ·x)=(y ·z);
a plurality of ligands L here may also be linked to one another or L is optionally linked to L′ via any desired bridge V and thus form a tridentate, tetradentate, pentadentate or hexadentate ligand system;
furthermore, a substituent R may also additionally be coordinated to the metal,
wherein the substituent R in the ortho-position to the metal coordination represents a group which is likewise coordinated to the metal M.
7. A compound selected from the compounds of the following formulae (17) to (22),
M is a transition metal;
Q is on each occurrence, identically or differently, N;
X is on each occurrence, identically or differently, CR or N;
Y is on each occurrence, identically or differently, a substituted or unsubstituted diatomic bridge containing, as bridge atoms, two atoms selected, identically or differently on each occurrence, from the group consisting of C, N, O, S, Si or P;
W is on each occurrence, identically or differently, CR, N, CR═CR or CR═N if Q stands for N, with the proviso that W stands for CR═CR or CR═N if Y stands for CR═CR or for CR═N;
or W is NR if Q stands for C;
Z is C if W in this ligand stands for CR═CR or CR═N; or one Z stands for C and the other Z stands for N if W in this ligand stands for CR or N or NR;
R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 1 ) 2 , CN, NO 2 , OH, COON, 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 is optionally substituted by one or more radicals R 1 , where one or more non-adjacent CH 2 groups is optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, NR 1 , O, S or CONR 1 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case be substituted by one or more radicals R′, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R′, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R′, 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 1 ; two adjacent radicals R here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
R′ 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 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 o tionall 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 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 or more adjacent radicals R 2 here may form a mono- or polycyclic, aliphatic ring system with one another;
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, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R 2 here may also form a mono- or polycyclic, aliphatic ring system with one another;
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;
a plurality of ligands L here may also be linked to one another or L is optionally linked to L′ via any desired bridge V and thus form a tridentate, tetradentate, pentadentate or hexadentate ligand system;
furthermore, a substituent R may also additionally be coordinated to the metal;
V represents a bridging unit containing 1 to 80 atoms from the third, fourth, fifth and/or sixth main group or a 3- to 6-membered homo- or heterocycle which covalently bonds the part-ligands L to one another or L to L′.
8. The compound according to claim 1 , wherein L′ is selected, identically or differently on each occurrence, from the group consisting of carbon monoxide, nitrogen monoxide, alkylcyanides, arylcyanides, alkylisocyanides, arylisocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, the halides F − , Cl − , Br − and I − , alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcoholates, amides, carboxylates, aryl groups, O 2− , S 2− , carbides, nitrenes, N 3− , diamines, imines, diimines, diphosphines, 1,3-diketonates 3-ketonates, salicyliminates dialcoholates, dithiolates, borates of nitrogen-containing heterocycles, η 5 -cyclopentadienyl, η 5 -pentamethyl-cyclopentadienyl, η 6 -benzene or η 7 -cycloheptatrienyl, each of which is optionally substituted by one or more radicals R, or ligands which have with the metal a cyclometallated five-membered ring or six-membered ring having at least one metal-carbon bond.
9. A process for the preparation of the compound according to claim 1 which comprises reacting the ligand with metal alkoxides of the formula (64), with metal ketoketonates of the formula (65), with metal halides of the formula (66) or with dimeric metal complexes of the formula (67),
where the symbols M, m, n and R have the meanings indicated in claim 1 and Hal=F, Cl, Br or I.
10. A formulation comprising at least one compound according to claim 1 and at least one solvent.
11. The formulation as claimed in claim 10 , wherein the formulation is a solution, a dispersion or a mini-emulsion.
12. An electronic device comprises the compound according to claim 1 .
13. An electronic device comprising at least one compound according to claim 1 in at least one layer and wherein the device is selected from the group consisting of an organic electroluminescent device, an organic light-emitting transistor, an organic light-emitting electrochemical cell, an organic light-emitting electrochemical transistor, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, an organic plasmon emitting device or an organic laser diode.
14. An electronic device comprising the compound according to claim 1 as emitting compound in one or more emitting layers and the electronic device is an organic electroluminescent device or organic light-emitting electrochemical cell.
15. The compound according to claim 1 , wherein the moiety of the formula ( 2 ) is selected from the structures of the formulae (9) and (10),
where the symbols and indices used have the meanings given in cm 1 .
16. The compound according to claim 1 , wherein M is iridium or platinum.