Electroluminescent metal complexes with triazoles and benzotriazoles
This invention relates to electroluminescent metal complexes with triazoles and benzotriazoles, respectively of the formula a process for their preparation, electronic devices comprising the metal complexes and their use in electronic devices, especially organic light emitting diodes (OLEDs), as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.
1. A compound of formula (VIa), (VIb), (VIIa), (VIIb), (VIIc), (VIId), (VIIIa) or (VIIIb)
wherein
M 2 is Rh, Re or Ir;
M 4 is Pd or Pt;
Q 1 and Q 2 are independently of each other hydrogen, C 1 -C 24 alkyl or C 6 -C 18 aryl which is optionally substituted by G;
L is a bidentate ligand;
A 11 , A 12 , A 13 , A 14 , A 15 and A 16 are independently of each other H, CN, halogen, C 1 -C 24 alkyl, C 1 -C 24 perfluoroalkyl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, C 6 -C 18 aryl, —NR 25 R 26 , —CONR 25 R 26 , —COOR 27 or C 2 -C 10 heteroaryl which is optionally substituted by G;
A 21 , A 22 , A 23 and A 24 are independently of each other hydrogen, CN, halogen, C 1 -C 24 alkyl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, C 1 -C 24 perfluoroalkyl, C 6 -C 18 aryl which is optionally substituted by G, —NR 25 R 26 , —CONR 25 R 26 , —COOR 27 or C 2 -C 10 heteroaryl which is optionally substituted by G; or
A 22 and A 23 are a group of formula
wherein A 41 , A 42 , A 43 , A 44 , A 45 and A 46 are independently of each other H, halogen, CN, C 1 -C 24 alkyl, C 1 -C 24 perfluoroalkyl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, C 6 -C 18 aryl which may optionally be substituted by G, —NR 25 R 26 , —CONR 25 R 26 , —COOR 27 or C 2 -C 10 heteroaryl;
R 25 and R 26 are independently of each other C 6 -C 18 aryl, C 7 -C 18 aralkyl or C 1 -C 24 alkyl, R 27 is C 1 -C 24 alkyl, C 6 -C 18 aryl or C 7 -C 18 aralkyl;
G is C 1 -C 18 alkyl, —OR 305 , —SR 305 , —NR 305 R 306 , —CONR 305 R 306 or —CN, wherein R 305 and R 306 are independently of each other C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy, C 1 -C 18 alkyl or C 1 -C 18 alkyl which is interrupted by —O—; or
R 305 and R 306 together form a five or six membered ring;
R 42 is hydrogen, C 1 -C 24 alkyl, CN, C 1 -C 24 alkyl which is substituted by halogen, C 6 -C 18 -aryl, C 6 -C 18 aryl which is substituted by C 1 -C 12 alkyl or C 1 -C 8 alkoxy,
R 43 is hydrogen, CN, halogen, C 1 -C 24 alkyl which is substituted by F, C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 12 alkyl, C 1 -C 8 alkoxy, —CONR 25 R 26 , —COOR 27 ,
wherein
E 2 is —S—, —O— or —NR 25′ —, wherein R 25′ is C 1 -C 24 alkyl or C 6 -C 10 aryl,
A 11′ , A 12′ , A 13′ and A 14′ are independently of each other H, halogen, CN, C 1 -C 24 alkyl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, —NR 25 R 26 , —CONR 25 R 26 or —COOR 27 ,
R 110 is H, CN, C 1 -C 24 alkyl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, —NR 25 R 26 , —CONR 25 R 26 or —COOR 27 or
R 42 and R 43 are a group of formula
wherein A 41 , A 42 , A 43 , A 44 , A 45 and A 46 are independently of each other H, halogen, CN, C 1 -C 24 alkyl, C 1 -C 24 perfluoroalkyl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, C 6 -C 18 aryl which may optionally be substituted by G, —NR 25 R 26 , —CONR 25 R 26 , —COOR 27 or C 2 -C 10 heteroaryl;
R 44 is hydrogen, CN, C 1 -C 24 alkyl, C 1 -C 24 alkyl which is substituted by halogen, C 6 -C 18 -aryl, C 6 -C 18 -aryl which is substituted by C 1 -C 12 alkyl or C 1 -C 8 alkoxy and
R 45 is hydrogen, CN, C 1 -C 24 alkyl, C 1 -C 24 alkyl which is substituted halogen, C 6 -C 18 -aryl, C 6 -C 18 -aryl which is substituted by C 1 -C 12 alkyl or C 1 -C 8 alkoxy.
2. A compound according to claim 1 wherein the bidentate ligand L is a compound of formula
wherein the ring A,
represents an optionally substituted aryl group which can optionally contain heteroatoms,
the ring B,
represents an optionally substituted nitrogen containing aryl group, which can optionally contain further heteroatoms, or the ring A may be taken with the ring B binding to the ring A to form a ring of formula
wherein R 206 , R 207 , R 208 , and R 209 are independently of each other hydrogen, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, aryl, heteroaryl, C 1 -C 24 alkoxy, C 1 -C 24 alkylthio, cyano, acyl, alkyloxycarbonyl, a nitro group or a halogen atom; 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; and the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group represented by R 206 , R 207 , R 208 and R 209 may be substituted.
3. A compound according to claim 1
wherein
L is a bidentate ligand selected from 3-(diphenylphosphino)-1-oxypropane, 1,1-bis(trifluoromethyl)-2-(diphenylphosphino)-ethoxide,
or L is a bidentate ligand selected from
wherein
R 11 and R 15 are independently of each other hydrogen, C 1 -C 8 alkyl, C 6 -C 18 aryl, C 2 -C 10 heteroaryl or C 1 -C 8 perfluoroalkyl,
R 12 and R 16 are independently of each other hydrogen or C 1 -C 8 alkyl and
R 13 and R 17 are independently of each other hydrogen, C 1 -C 8 alkyl, C 6 -C 18 aryl, C 2 -C 10 heteroaryl, C 1 -C 8 perfluoroalkyl or C 1 -C 8 alkoxy and
R 14 is C 1 -C 8 alkyl, C 6 -C 10 aryl or C 7 -C 11 aralkyl,
R 18 is C 6 -C 10 aryl,
R 19 is C 1 -C 8 alkyl,
R 20 is C 1 -C 8 alkyl or C 6 -C 10 aryl,
R 21 is hydrogen, C 1 -C 8 alkyl or C 1 -C 8 alkoxy which may be partially or fully fluorinated,
A 11 is hydrogen,
A 12 is hydrogen,
A 13 is hydrogen,
A 14 is hydrogen or C 6 -C 18 aryl,
A 15 is hydrogen or C 6 -C 18 aryl,
A 16 is hydrogen,
A 21 is hydrogen,
A 22 is hydrogen or C 6 -C 10 aryl,
A 23 is hydrogen or C 6 -C 10 aryl,
A 24 is hydrogen,
R 42 is H, F, C 1 -C 4 alkyl, C 1 -C 8 alkoxy or C 1 -C 4 perfluoroalkyl,
R 43 is H, F, C 1 -C 4 alkyl, C 1 -C 8 alkoxy, C 1 -C 4 perfluoroalkyl or C 6 -C 10 aryl,
R 44 is H, F, C 1 -C 4 alkyl, C 1 -C 8 alkoxy or C 1 -C 4 perfluoroalkyl,
R 45 is H, F, C 1 -C 4 alkyl, C 1 -C 8 alkoxy or C 1 -C 4 perfluoroalkyl and
R 46 is C 1 -C 8 alkyl, C 6 -C 18 aryl, C 1 -C 8 alkoxy or C 6 -C 18 aryl which is substituted by C 1 -C 8 alkyl.
4. A compound according to claim 3 of formulae
Cpd.
R 45
R 44
R 43
R 42
Q 1
Q 2
C-1
H
H
H
H
H
H
C-2
F
H
H
H
H
H
C-3
H
H
F
H
H
H
C-4
F
H
F
H
H
H
C-5
F
H
H
F
H
H
C-6
H
H
CF 3
H
H
H
C-7
H
CF 3
H
CF 3
H
H
C-8
CF 3
H
H
H
H
H
C-9
H
CH 3
H
CH 3
H
H
C-10
H
H
CH 3
H
H
H
C-11
H
H
Ph
H
H
H
C-12
H
H
Ome
H
H
H
C-13
CH 3
CH 3
H
H
H
H
C-14
CH 3
H
CH 3
H
H
H
C-15
H
H
Ph
H
H/Ph 1)
Ph/H 1)
C-16
H
H
t-Bu
H
H
H
1) mixture of isomers
Cpd.
L
R 45
R 44
R 43
R 42
Q 1
Q 2
D-1
A 2)
H
H
H
H
H
H
D-2
A 2)
F
H
H
H
H
H
D-3
A 2)
H
H
F
H
H
H
D-4
A 2)
F
H
F
H
H
H
D-5
A 2)
F
H
H
F
H
H
D-6
A 2)
H
H
CF 3
H
H
H
D-7
A 2)
H
CF 3
H
CF 3
H
H
D-8
A 2)
CF 3
H
H
H
H
H
D-9
A 2)
H
CH 3
H
CH 3
H
H
D-10
A 2)
H
H
CH 3
H
H
H
D-11
A 2)
H
H
Ph
H
H
H
D-12
A 2)
H
H
OMe
H
H
H
D-13
A 2)
CH 3
CH 3
H
H
H
H
D-14
A 2)
CH 3
H
CH 3
H
H
H
D-15
A 2)
H
H
Ph
H
H/Ph 1)
Ph/H 1)
D-16
A 2)
H
t-Bu
H
H
H
H
D-17
B 2)
H
H
H
H
H
H
D-18
B 2)
F
H
H
H
H
H
D-19
B 2)
H
H
F
H
H
H
D-20
B 2)
F
H
F
H
H
H
D-21
B 2)
F
H
H
F
H
H
D-22
B 2)
H
H
CF 3
H
H
H
D-23
B 2)
H
CF 3
H
CF 3
H
H
D-24
B 2)
CF 3
H
H
H
H
H
D-25
B 2)
H
CH 3
H
CH 3
H
H
D-26
B 2)
H
H
CH 3
H
H
H
D-27
B 2)
H
H
Ph
H
H
H
D-28
B 2)
H
H
OMe
H
H
H
D-29
B 2)
CH 3
CH 3
H
H
H
H
D-30
B 2)
CH 3
H
CH 3
H
H
H
D-31
B 2)
H
H
Ph
H
H/Ph 1)
Ph/H 1)
D-32
B 2)
H
t-Bu
H
H
H
H
D-33
C 2)
H
H
H
H
H
H
D-34
C 2)
F
H
H
H
H
H
D-35
C 2)
H
H
F
H
H
H
D-36
C 2)
F
H
F
H
H
H
D-37
C 2)
F
H
H
F
H
H
D-38
C 2)
H
H
CF 3
H
H
H
D-39
C 2)
H
CF 3
H
CF 3
H
H
D-40
C 2)
CF 3
H
H
H
H
H
D-41
C 2)
H
CH 3
H
CH 3
H
H
D-42
C 2)
H
H
CH 3
H
H
H
D-43
C 2)
H
H
Ph
H
H
H
D-44
C 2)
H
H
OMe
H
H
H
D-45
C 2)
CH 3
CH 3
H
H
H
H
D-46
C 2)
CH 3
H
CH 3
H
H
H
D-47
C 2)
H
H
Ph
H
H/Ph 1)
Ph/H 1)
D-48
C 2)
H
t-Bu
H
H
H
H
D-49
D 2)
H
H
H
H
H
H
D-50
D 2)
F
H
H
H
H
H
D-51
D 2)
H
H
F
H
H
H
D-52
D 2)
F
H
F
H
H
H
D-53
D 2)
F
H
H
F
H
H
D-54
D 2)
H
H
CF 3
H
H
H
D-55
D 2)
H
CF 3
H
CF 3
H
H
D-56
D 2)
CF 3
H
H
H
H
H
D-57
D 2)
H
CH 3
H
CH 3
H
H
D-58
D 2)
H
H
CH 3
H
H
H
D-59
D 2)
H
H
Ph
H
H
H
D-60
D 2)
H
H
OMe
H
H
H
D-61
D 2)
CH 3
CH 3
H
H
H
H
D-62
D 2)
CH 3
H
CH 3
H
H
H
D-63
D 2)
H
H
Ph
H
H/Ph 1)
Ph/H 1)
D-64
D 2)
H
t-Bu
H
H
H
H
D-65
E 2)
H
H
H
H
H
H
D-66
E 2)
F
H
H
H
H
H
D-67
E 2)
H
H
F
H
H
H
D-68
E 2)
F
H
F
H
H
H
D-69
E 2)
F
H
H
F
H
H
D-70
E 2)
H
H
CF 3
H
H
H
D-71
E 2)
H
CF 3
H
CF 3
H
H
D-72
E 2)
CF 3
H
H
H
H
H
D-73
E 2)
H
CH 3
H
CH 3
H
H
D-74
E 2)
H
H
CH 3
H
H
H
D-75
E 2)
H
H
Ph
H
H
H
D-76
E 2)
H
H
OMe
H
H
H
D-77
E 2)
CH 3
CH 3
H
H
H
H
D-78
E 2)
CH 3
H
CH 3
H
H
H
D-79
E 2)
H
H
Ph
H
H/Ph 1)
Ph/H 1)
D-80
E 2)
H
t-Bu
H
H
H
H
1) mixture of isomers
5. An organic electronic device, comprising an emitting layer wherein the emitting layer comprises a compound according to claim 1 .
6. A device according to claim 5 , further comprising a hole transport layer selected from polyvinyl-carbazol, N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine (ETPD), tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA), a-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB), N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB), porphyrinic compounds and combinations thereof.