Metal complexes
View Patent ↗The present invention describes new types of metal complexes. Such compounds can be used as functional materials in a series of different types of applications which can be classified within the electronics industry in the widest sense. The inventive compounds are described by the formulae (1) and (4).
1. A compound of the formula (1)
M(L) n (L′) m (L″) 0 Formula (1)
containing a part-structure M(L) n of the formula (2)
wherein the symbols and indices used are:
M at each instance is Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt or Au;
Y is the same or different at each instance and is SiR 1 2 , NR 1 , PR 1 , P(O)R 1 , or O;
D is the same or different at each instance and is a carbon atom or a nitrogen atom which coordinates to the metal, with the proviso that one D per ligand is a carbon atom and the other is a nitrogen atom;
E is C;
Cy1 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group which is bonded to the metal M via an atom D and which also has a single bond to the part-cycle Cy2 and a single bond to the Y group, wherein the substituent is R;
Cy2 is the same or different at each instance and is a substituted or unsubstituted 6-member heteroaryl group wherein the heteroatom is N, which is bonded via an atom D to the metal M and which also has a single bond to the cycle Cy1 and a common edge with the part-cycle Cy3, wherein the substituent is R;
Cy3 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group which has a single bond to the Y group and a common edge with the part-cycle Cy2, wherein the substituent is R;
R is the same or different at each instance and is H, F, Cl, Br, I, OH, NO 2 , CN, a straight-chain, branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH 2 groups may be replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , Ge(R 1 ) 2 , Sn(R 1 ) 2 , —O—, —S—, —NR 1 —, —(C═O)—, —(C═NR 1 )—, —P═O(R 1 )— or —CONR 1 — and where one or more hydrogen atoms is optionally replaced by F, or an aryl, heteroaryl, aryloxy or heteroaryloxy group which has from 1 to 14 carbon atoms and is optionally substituted by one or more nonaromatic R radicals, where a plurality of substituents R, both on the same ring and on different rings, may in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
R 1 is the same or different at each instance and is H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms;
n is 1, 2 or 3;
the ligands L′ and L″ in formula (1) are monoanionic, bidentate chelating ligands, and m and o are the same or different at each instance and are 0, 1 or 2.
2. The compound as claimed in claim 1 , comprising the part-structure of the formula (2a):
wherein Y, R 1 , L′ and L″ and n are each defined as described in claim 1 , and the further symbols are:
M is Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt or Au;
D is the same or different at each instance and is a carbon atom or a nitrogen atom, with the proviso that one D is a carbon atom and the other D is a nitrogen atom;
X is CR;
E is C;
R is the same or different at each instance and is H, F, Cl, Br, I, OH, NO 2 , CN, a straight-chain, branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH 2 groups may be replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , Ge(R 1 ) 2 , Sn(R 1 ) 2 , —O—, —S—, —NR 1 —, —(C═O)—, —(C═NR 1 )—,—P═O(R 1 )— or —CONR 1 — and where one or more hydrogen atoms is optionally replaced by F, or an aryl, heteroaryl, aryloxy or heteroaryloxy group which has from 1 to 14 carbon atoms and is optionally substituted by one or more nonaromatic R radicals, where a plurality of substituents R, both on the same ring and on different rings, may in turn form a further mono- or polycyclic, aliphatic or aromatic ring system.
3. The compound as claimed in claim 2 , wherein the compound is of the formula (1a),
M(L) n (L′) m (L″) 0 Formula (1a)
containing at least one part-structure M(L) n of the formula (2b), identically or differently at each instance,
and optionally containing a part-structure M(L′) m of the formula (3), identically or differently at each instance
wherein M, X, Y, R, R 1 , L″, n, m and o are each defined as described in claim 2 and the further symbols and indices are each defined as follows:
D is N; and
A is the same or different at each instance and is —CR═CR—, —N═CR—, —P═CR—, —N═N—, —P═N—, NR, O or S.
4. The compound as claimed in claim 1 , wherein M is Rh, Ir, Pd or Pt.
5. The compound as claimed in claim 1 , wherein n is 2 or 3.
6. The compound as claimed in claim 1 , wherein Y is NR 1 , P(O)R 1 , or O.
7. The compound as claimed in claim 1 , wherein
R is the same or different at each instance and is H, F, a straight-chain, branched or cyclic alkyl or alkoxy group having from 1 to 4 carbon atoms, where one or more hydrogen atoms is optionally replaced by F, or an aryl or heteroaryl group which has from 1 to 6 carbon atoms and is optionally substituted by one or more nonaromatic R radicals, where a plurality of substituents R, both on the same ring and on different rings, together may in turn form a further aliphatic or aromatic, mono- or polycyclic ring system.
8. A compound of the formula (4)
wherein
E is C;
Cy1 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group which is bonded to the metal M via an atom D′ and which also has a single bond to the part-cycle Cy2 and a single bond to the Y group, wherein the substituent is R;
Cy2 is the same or different at each instance and is a substituted or unsubstituted 6-member heteroaryl group wherein the heteroatom is N, which is bonded via an atom D′ to the metal M and which also has a single bond to the cycle Cy1 and a common edge with the part-cycle Cy3, wherein the substituent is R;
Cy3 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group which has a single bond to the Y group and a common edge with the part-cycle Cy2, wherein the substituent is R;
Y′ is the same or different at each instance and is SiR 1 2 , PR 1 , or P(O)R 1 ;
R is the same or different at each instance and is H, F, Cl, Br, I, OH, NO 2 , CN, a straight-chain, branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH 2 groups may be replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , Ge(R 1 ) 2 , Sn(R 1 ) 2 , —O—, —S—, —NR 1 —, —(C═O)—, —(C═NR 1 )—, —P═O(R 1 )— or —CONR 1 — and where one or more hydrogen atoms is optionally replaced by F, or an aryl, heteroaryl, aryloxy or heteroaryloxy group which has from 1 to 14 carbon atoms and is optionally substituted by one or more nonaromatic R radicals, where a plurality of substituents R, both on the same ring and on different rings, may in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
R 1 is the same or different at each instance and is H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms; and
D′ is the same or different at each instance and is C—H or N, with the proviso that one symbol D′ is C—H and the other symbol D′ is N.
9. The compound as claimed in claim 8 , wherein the compound is of the formula (4a)
where X is CR, and the other symbols are each as defined in claim 8 .
10. The compound as claimed in claim 8 , wherein the compound is of the formula (4b)
wherein X is CR.
11. A process for preparing the compound as claimed in claim 1 which comprises reacting the compounds of the formula (4), (4a) or (4b)
with metal alkoxides of the formula (5), with metal ketoketonates of the formula (6) or mono- or polycyclic metal halides of the formula (7), (8) or (9), or with iridium compounds which bear both alkoxide and/or halide and/or hydroxyl and ketoketonate radicals
wherein
E is C;
Cy1is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group which is bonded to the metal M via an atom D and which also has a single bond to the part-cycle Cy2and a single bond to the Y group, wherein the substituent is R;
Cy2is the same or different at each instance and is a substituted or unsubstituted 6-member heteroaryl group wherein the heteroatom is N, which is bonded via an atom D to the metal M and which also has a single bond to the cycle Cy1and a common edge with the part-cycle Cy3, wherein the substituent is R;
Cy3 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group which has a single bond to the Y group and a common edge with the part-cycle Cy2, wherein the substituent is R;
Y′ is the same or different at each instance and is SiR 1 2 , PR 1 , or P(O)R 1 ;
R is the same or different at each instance and is H, F, Cl, Br, I, OH, NO 2 , CN, a straight-chain, branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH 2 groups may be replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , Ge(R 1 ) 2 , Sn(R 1 ) 2 , —O—, —S—, —NR 1 —, —(C═O)—, —(C═NR 1 )—, —P═O(R 1 )— or —CONR 1 — and where one or more hydrogen atoms is optionally replaced by F, or an aryl, heteroaryl, aryloxy or heteroaryloxy group which has from 1 to 14 carbon atoms and is optionally substituted by one or more nonaromatic R radicals, where a plurality of substituents R, both on the same ring and on different rings, may in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
D′ is the same or different at each instance and is C—H or N, with the proviso that one symbol D′ is C—H and the other symbol D′ is N;
X is CR;
M at each instance is Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt or Au;
R 1 is the same or different at each instance and is H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms;
P is 1 or 2 and
Hal is F, Cl, Br, or I.
12. The compound as claimed in claim 1 , wherein the compound has a purity (determined by means of 1 H NMR and/or HPLC) of more than 99%.
13. A conjugated, part-conjugated or nonconjugated polymer or dendrimer containing one or more of the compounds as claimed in claim 1 .
14. A conjugated, part-conjugated or nonconjugated polymer or dendrimer containing one or more of the compounds as claimed in claim 2 .
15. The polymer or dendrimer as claimed in claim 14 , wherein at least one R is a bond to the polymer or dendrimers.
16. The polymer as claimed in claim 13 , wherein the polymer is selected from the group of polyfluorene, polyspirobifluorene, polyparaphenylene, polycarbazole, polyvinylcarbazole, polythiophene, polyketone or a mixture of these polymers.
17. An electronic component comprising at least one compound as claimed in claim 1 .
18. The electronic component of claim 17 , wherein the electronic component is an organic light-emitting diode (OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic solar cell (O-SC) or an organic laser diode (O-laser).
19. A compound of the formula (1)
M(L) n (L′) m (L″) 0 Formula (1)
containing a part-structure M(L) n of the formula (2)
wherein the symbols and indices used are:
M at each instance is Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt or Au;
Y is the same or different at each instance and is SiR 1 2 , NR 1 , PR 1 , P(O)R 1 , or O;
D is the same or different at each instance and is a carbon atom or a nitrogen atom which coordinates to the metal, with the proviso that one D per ligand is a carbon atom and the other is a nitrogen atom;
E is C;
Cy1 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group, which is bonded to the metal M via an atom D and which also has a single bond to the part-cycle Cy2 and a single bond to the Y group, wherein the substituent is R;
Cy2 is the same or different at each instance and is a substituted or unsubstituted 6-member heteroaryl group wherein the heteroatom is N, which is bonded via an atom D to the metal M and which also has a single bond to the cycle Cy1 and a common edge with the part-cycle Cy3, wherein the substituent is R;
Cy3 is the same or different at each instance and is a substituted or unsubstituted 6-membered aryl group, which has a single bond to the Y group and a common edge with the part-cycle Cy2, wherein the substituent is R;
R is the same or different at each instance and is H, F, Cl, Br, I, OH, NO 2 , CN, a straight-chain, branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH 2 groups may be replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , Ge(R 1 ) 2 , Sn(R 1 ) 2 , —O—, —S—, —NR 1 —, —(C═O)—, —(C═NR 1 )—, —P═O(R 1 )— or —CONR 1 — and where one or more hydrogen atoms is optionally replaced by F, or an aryl, heteroaryl, aryloxy or heteroaryloxy group which has from 1 to 14 carbon atoms and is optionally substituted by one or more nonaromatic R radicals;
R 1 is the same or different at each instance and is H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms;
n is 1, 2 or 3;
the ligands L′ and L″ in formula (1) are monoanionic, bidentate chelating ligands, and m and o are the same or different at each instance and are 0, 1 or 2.