Electroluminescent metal complex

A compound of formula (III) or tautomeric forms thereof,

• wherein
• is a bidentate C,N-binding ligand, CyC and CyN are interlinked by a chemical bond,
• n is 1,
• M is Ir and m is 2 or
• M is Pt and m is 1;
• and
• wherein the moiety
• is selected from a group consisting of

Compound of the formula I

• [LDH]nM[L]m (I),
• wherein
• n is an integer 1,
• M is Co, Fe, Ir, or Rh, and
• m is 2, or
• M is Ni, Rh, Ru, Pd, or Pt, and
• m is 1,
• LDH is a bidentate ligand of the formula II
• wherein
• W is selected from O, S, NR4, CR5R6,
• X is N or CH,
• Y is selected from O, S, NR8;
• R1, R2 independently are selected from H, unsubstituted or substituted C1-C8alkyl, unsubstituted or substituted phenyl, halogen, C1-C8alkoxy, COR, COOR, SO2R, CN, NHR, NRR′;
• or the neighbouring residues R1 and R2 form an organic bridging group completing, together with the carbon atoms they are bonding to, an annellated phenyl ring, which optionally may be substituted;
• R4, R5, R6 independently are H, unsubstituted or substituted C1-C8alkyl, unsubstituted or substituted C2-C8alkenyl, unsubstituted or substituted phenyl;
• R3 is H, unsubstituted or substituted C1-C8alkyl, unsubstituted or substituted C2-C8alkenyl, unsubstituted or substituted phenyl;
• and
• any substituent, if present, is selected from halogen, C1-C8alkyl, C1-C8alkoxy, phenyl, phenyloxy, COR, OCOR, COOR, SO2R, CN, NHR, NRR′;
• and
• R and R′ independently are selected from C1-C6alkyl, and R may also be hydrogen;
• R8 is H, SO2—R11, CO—R11, where Rii is C1-C12alkyl, C1-C12haloalkyl, phenyl, phenyl substituted by halogen;
• and
• L is a bidentate ligand and is selected from the ligands:
• a) of formula
• wherein R6, R7, R8, and R9 are independently of each other hydrogen, C1-C24alkyl, C2-C24alkenyl, C2-C24alkynyl, aryl, heteroaryl, C1-C24alkoxy, C1-C24alkylthio, cyano, acyl, alkyloxycarbonyl, a nitro group, or a halogen atom;
• or
• two R6, R7, R8, and R9, which are adjacent to each other, together form a group
• wherein R205, R206, R207 and R208 are independently of each other H, or C1-C8alkyl,
• the ring A represents an optionally substituted aryl or heteroaryl group;
• or the ring A may be taken with the pyridyl group binding to the ring A to form a ring;
• the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group represented by R6, R7, R8, and R9 may be substituted;
• b) of the formula
• wherein Y′ is S, O, NR200, wherein
• R200 is hydrogen, cyano, C1-C4alkyl, C2-C4alkenyl, optionally substituted C6-C10aryl, —(CH2)r—Ar wherein Ar is an optionally substituted C6-C10aryl, a group —(CH2)r′X20, wherein r′ is an integer of 1 to 5, X20 is halogen, hydroxy, —O—C1-C4alkyl, di(C1-C4alkyl)amino, amino, or cyano;
• a group —(CH2)rOC(O)(CH2)r″CH3, wherein r is 1, or 2, and r″ is 0, or 1;
• —NH-Ph, —C(O)CH3, —CH2—O—(CH2)2—Si(CH3)3, or
• c) of the formula
• wherein
• Q1 and Q2 are independently of each other hydrogen, C1-C24alkyl, or C6-C18aryl,
• A21 is hydrogen, halogen, C1-C4alkoxy, or C1-C4alkyl,
• A22 is hydrogen, halogen, C1-C12alkoxy, C1-C12alkyl, or C6-C10aryl,
• A23 is hydrogen, halogen, C1-C12alkoxy, C1-C12alkyl, or C6-C10aryl,
• A24 is hydrogen, halogen, C1-C4alkoxy, or C1-C4alkyl, or
• A22 and A23, or A23 and A24 together form a group
• wherein R205, R206, R207 and R208 are independently of each other H, halogen, C1-C12alkoxy, or C1-C12alkyl,
• R42 is H, halogen, C1-C12alkyl, C1-C12alkoxy, or C1-C4perfluoroalkyl,
• R43 is H, halogen, C1-C12alkyl, C1-C12alkoxy, C1-C4perfluoroalkyl, C7-C15aralkyl, or C6-C10aryl,
• R44 is H, halogen, C1-C12alkyl, C1-C12alkoxy, C6-C10aryl, C7-C15aralkyl, or C1-C4perfluoroalkyl,
• R45 is H, halogen, C1-C12alkyl, C1-C12alkoxy, or C1-C4perfluoroalkyl;
• d1) of the formula
• wherein
• n is 0, 1 or 2,
• A12, A14, A16, A21, A22, A23, and A24 are independently of each other hydrogen, CN, halogen, C1-C24alkyl, C1-C24alkoxy, C1-C24alkylthio, C1-C24perfluoroalkyl, C6-C18aryl, which is optionally substituted by G;
• —NR25R26, —CONR25R26, or —COOR27, or C2-C10heteroaryl, which is optionally substituted by G;
• or C5-C12cycloalkyl, C5-C12cycloalkoxy, C5-C12cycloalkylthio, each of which is optionally substituted by G;
• 2 adjacent radicals A14, A17 or A17, A16, bonding to vicinal atoms, together are a group of formula
• wherein A41,A42, A43, A44, A45, and A46 are independently of each other H, halogen, CN, C1-C24alkyl, C1-C24perfluoroalkyl, C1-C24alkoxy, C1-C24alkylthio, C6-C18aryl, which may optionally be substituted by G, —NR25R26, —CONR25R26, or —COOR27, or C2-C10heteroaryl;
• A11, A13, A15, A′21, A′22, A′23 and A′24 are independently of each other hydrogen or C1-C24alkyl;
• or 2 adjacent radicals A11, A12;
• A13, A14;
• A15, A16;
• A′21, A21;
• A′22, A22;
• A′23, A23;
• A′24, A24, bonding to the same carbon atom, together are ═O or ═NR25 or ═N—OR25 or ═N—OH;
• R25 and R26 are independently of each other C6-C18aryl, C7-C18aralkyl, or C1-C24alkyl, R27 is C1-C24alkyl, C6-C18aryl, or C7-C18aralkyl;
• or
• d2) of the formula
• wherein
• A′22 and A′23 are independently of each other hydrogen or C1-C24alkyl;
• 2 adjacent radicals A18, A22 and A23, A19, bonding to vicinal atoms, together are a group of formula
• wherein A41, A42, A43, A44, A45, and A46 are independently of each other H, halogen, CN, C1-C24alkyl, C1-C24perfluoroalkyl, C1-C24alkoxy, C1-C24alkylthio, C6-C18aryl, which may optionally be substituted by G, —NR25R26, —CONR25R26, or —COOR27, or C2-C10heteroaryl;
• R25 and R26 are independently of each other C6-C18aryl, C7-C18aralkyl, or C1-C24alkyl, R27 is C1-C24alkyl, C6-C18aryl, or C7-C18aralkyl;
• and
• for d1) and d2):
• Y1, Y2 and Y3 are independently of each other a group of formula
• wherein
• R41 is the bond to M,
• R71 is the bond to M,
• R42 is hydrogen, or C1-C24alkyl, CN, C1-C24alkyl, which is substituted by halogen, C6-C18-aryl, C6-C18-aryl substituted by C1-C12alkyl, or C1-C8alkoxy,
• R43 is hydrogen, CN, halogen, C1-C24alkyl substituted by F, C6-C18aryl, C6-C18aryl substituted by C1-C12alkyl, or C1-C8alkoxy, —CONR25R26, —COOR27,
• wherein
• E2 is —S—, —O—, or —NR25′—, wherein R25′ is C1-C24alkyl, or C6-C10aryl,
• or R42 and R43 are a group of formula
• wherein A41, A42, A43, A44, A45, and A46 are independently of each other H, halogen, CN, C1-C24alkyl, C1-C24perfluoroalkyl, C1-C24alkoxy, C1-C24alkylthio, C6-C18aryl, which may optionally be substituted by G, —NR25R26, —CONR25R26, or —COOR27, or C2-C10heteroaryl;
• R44 is hydrogen, CN or C1-C24alkyl, C1-C24alkyl substituted by F, halogen, C6-C18-aryl, C6-C18-aryl substituted by C1-C12 alkyl, or C1-C8alkoxy,
• R45 is hydrogen, CN or C1-C24alkyl, C1-C24alkyl substituted by F, halogen, C6-C18-aryl, C6-C18-aryl substituted by C1-C12alkyl, or C1-C8alkoxy,
• A11′, A12′, A13′, and A14′ are independently of each other H, halogen, CN, C1-C24alkyl, C1-C24alkoxy, C1-C24alkylthio, —NR25R26, —CONR25R26, or —COOR27,
• R68 and R69 are independently of each other C1-C24alkyl, which may be interrupted by one or two oxygen atoms,
• R70, R72, R73, R74, R75, R76, R90, R91, R92, and R93 are independently of each other H, halogen, CN, C1-C24alkyl, C6-C10aryl, C1-C24alkoxy, C1-C24alkylthio, —NR25R26, —CONR25R26, or —COOR27, wherein R25, R26 and R27 are as defined above and
• G is C1-C18alkyl, —OR305, —SR305, —NR305R306, —CONR305R306, or —CN, wherein R305 and R306 are independently of each other C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy;
• C1-C18alkyl, or C1-C18alkyl which is interrupted by —O—;
• or R305 and R306 together form a five or six membered ring;
• e) of formula
• wherein R6 is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4perfluoroalkyl, C1-C4alkoxy, or optionally substituted C6-C10aryl,
• R7 is hydrogen, halogen, C1-C4alkyl, C1-C4perfluoroalkyl, optionally substituted C6-C10aryl, or optionally substituted C6-C10perfluoroaryl,
• R8 is hydrogen, C1-C4alkyl, C1-C8alkoxy, C1-C4perfluoroalkyl, optionally substituted C6-C10aryl, or optionally substituted C6-C10perfluoroaryl,
• R9 is hydrogen, halogen, nitro, cyano, C1-C4alkyl, C1-C4perfluoroalkyl, C1-C4alkoxy, or optionally substituted C6-C10aryl,
• A10 is hydrogen, halogen, nitro, cyano, C1-C4alkyl, C2-C4alkenyl, C1-C4perfluoroalkyl, —O—C1-C4perfluoroalkyl, tri(C1-C4alkyl)silanyl, optionally substituted C6-C10aryl, or optionally substituted C6-C10perfluoroaryl,
• A11 is hydrogen, halogen, nitro, cyano, C1-C4alkyl, C2-C4alkenyl, C1-C4perfluoroalkyl, —O—C1-C4perfluoroalkyl, tri(C1-C4alkyl)silanyl, optionally substituted C6-C10aryl, or optionally substituted C6-C10perfluoroaryl,
• A12 is hydrogen, halogen, nitro, hydroxy, mercapto, amino, C1-C4alkyl, C2-C4alkenyl, C1-C4perfluoroalkyl, C1-C4alkoxy, —O—C1-C4perfluoroalkyl, —S—C1-C4alkyl, a group —(CH2)rX20, wherein r is 1, or 2, X20 is halogen, hydroxy, cyano, —O—C1-C4alkyl, di(C1-C4alkyl)amino, —CO2X21, wherein X21 is H, or C1-C4alkyl;
• —CH═CHCO2X22, wherein X22 is C1-C4alkyl;
• —CH(O), —SO2X23, —SOX23, —NC(O)X23, —NSO2X23, —NHX23, —N(X23)2, wherein X23 is C1-C4alkyl;
• tri(C1-C4alkyl)siloxanyl, optionally substituted —O—C6-C10aryl, cyclohexyl, optionally substituted C6-C10aryl, or optionally substituted C6-C10perfluoroaryl, and
• A13 is hydrogen, nitro, cyano, C1-C4alkyl, C2-C4alkenyl, C1-C4perfluoroalkyl, —O—C1-C4perfluoroalkyl, tri(C1-C4alkyl)silanyl, or optionally substituted C6-C10aryl.