IP Library › Granted Patent US 7,820,828

Granted Patent B2

US 7,820,828 · App. 11/629,573 · Granted Oct 26, 2010

Electroluminescent metal complexes with triazoles and benzotriazoles

Assignee: Ciba Specialty Chemicals Corp.

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Quick Facts

Patent No.: US 7,820,828
App. No.: 11/629,573
Granted: Oct 26, 2010
Kind: B2

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Abstract

This invention relates to electroluminescent metal complexes with triazoles and benzotriazoles, respectively of the formula (I) 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.

Claims (3474)

1. A compound of the formula (Va), (Vb), (Vc), (Vd), (Ve) or (Vf)

wherein

M 2 is Rh, Re or Ir;

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;

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 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

R 44 is hydrogen, CN or 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 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.

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, R 206 , R 207 , R 208 and R 209 may alkylthio group, acyl group, and alkyloxycarbonyl group represented by be substituted.

3. A compound according to claim 1

wherein

M 2 is Rh, Re or Ir,

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 s 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 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

A 24

A 23

A 22

A 21

A-1

A-2

A-3

A-4

A-5

A-6

CF 3

A-7

CF 3

A-8

CF 3

A-9

CH 3

A-10

CH 3

A-11

A-12

Ome

A-13

CH 3

A-14

CH 3

A-15

H/Ph 1)

Ph/H 1)

A-16

t-Bu

A-17

1) mixture of isomers

2) 2,4,4-trimethylpent-2-ylp

Cpd.

R 45

R 44

R 43

R 42

A 24

A 23

A 22

A 21

B-1

A 2)

B-2

A 2)

B-3

A 2)

B-4

A 2)

B-5

A 2)

B-6

A 2)

CF 3

B-7

A 2)

CF 3

B-8

A 2)

CF 3

B-9

A 2)

CH 3

B-10

A 2)

CH 3

B-11

A 2)

B-12

A 2)

OMe

B-13

A 2)

CH 3

B-14

A 2)

CH 3

B-15

A 2)

H/Ph 1)

Ph/H 1)

B-16

A 2)

t-Bu

B-17

B 2)

B-18

B 2)

B-19

B 2)

B-20

B 2)

B-21

B 2)

B-22

B 2)

CF 3

B-23

B 2)

CF 3

B-24

B 2)

CF 3

B-25

B 2)

CH 3

B-26

B 2)

CH 3

B-27

B 2)

B-28

B 2)

OMe

B-29

B 2)

CH 3

B-30

B 2)

CH 3

B-31

B 2)

H/Ph 1)

Ph/

H 1)

B-32

B 2)

t-Bu

B-33

C 2)

B-34

C 2)

B-35

C 2)

B-36

C 2)

B-37

C 2)

B-38

C 2)

CF 3

B-39

C 2)

CF 3

B-40

C 2)

CF 3

B-41

C 2)

CH 3

B-42

C 2)

CH 3

B-43

C 2)

B-44

C 2)

OMe

B-45

C 2)

CH 3

B-46

C 2)

CH 3

B-47

C 2)

H/Ph 1)

Ph/H 1)

B-48

C 2)

t-Bu

B-49

D 2)

B-50

D 2)

B-51

D 2)

B-52

D 2)

B-53

D 2)

B-54

D 2)

CF 3

B-55

D 2)

CF 3

B-56

D 2)

CF 3

B-57

D 2)

CH 3

B-58

D 2)

CH 3

B-59

D 2)

B-60

D 2)

OMe

B-61

D 2)

CH 3

B-62

D 2)

CH 3

B-63

D 2)

H/Ph 1)

Ph/H 1)

B-64

D 2)

t-Bu

B-65

B-66

B-67

B-68

1) mixture of isomers

3) 2,4,4-trimethylpent-2-yl

Cpd.

R 45

R 44

R 43

R 42

A 11

A 12

A 13

A 14

A 15

A 16

E-1

A 2)

CH 3

E-2

A 2)

E-3

A 2)

E-4

A 2)

E-5

A 2)

E-6

A 2)

E-7

A 2)

CF 3

E-8

A 2)

CF 3

E-9

A 2)

CF 3

E-10

A 2)

CH 3

E-11

A 2)

t-Bu

E-12

A 2)

E-13

A 2)

OMe

E-14

A 2)

CH 3

E-15

A 2)

CH 3

E-16

A 2)

H/Ph 1)

Ph/H 1)

E-17

B 2)

CH 3

E-18

B 2)

E-19

B 2)

E-20

B 2)

E-21

B 2)

E-22

B 2)

E-23

B 2)

CF 3

E-24

B 2)

CF 3

E-25

B 2)

CF 3

E-26

B 2)

CH 3

E-27

B 2)

t-Bu

E-28

B 2)

E-29

B 2)

OMe

E-30

B 2)

CH 3

E-31

B 2)

CH 3

E-32

B 2)

H/Ph 1)

Ph/H 1)

E-33

C 2)

CH 3

E-34

C 2)

E-35

C 2)

E-36

C 2)

E-37

C 2)

E-38

C 2)

E-39

C 2)

CF 3

E-40

C 2)

CF 3

E-41

C 2)

CF 3

E-42

C 2)

CH 3

E-43

C 2)

t-Bu

E-44

C 2)

E-45

C 2)

OMe

E-46

C 2)

CH 3

E-47

C 2)

CH 3

E-48

C 2)

H/Ph 1)

Ph/H 1)

E-49

D 2)

CH 3

E-50

D 2)

E-51

D 2)

E-52

D 2)

E-53

D 2)

E-54

D 2)

E-55

D 2)

CF 3

E-56

D 2)

CF 3

E-57

D 2)

CF 3

E-58

D 2)

CH 3

E-59

D 2)

t-Bu

E-60

D 2)

E-61

D 2)

OMe

E-62

D 2)

CH 3

E-63

D 2)

CH 3

E-64

D 2)

H/Ph 1)

Ph/H 1)

E-65

E 2)

E-65

E 2)

E-66

E 2)

E-66

E 2)

E-67

E 2)

E-67

E 2)

E-68

E 2)

E-68

E 2)

E-69

E 2)

E-69

E 2)

E-70

E 2)

CF 3

E-70

E 2)

E-71

E 2)

CF 3

E-71

E 2)

E-72

E 2)

CF 3

E-72

E 2)

E-73

E 2)

CH 3

E-73

E 2)

E-74

E 2)

CH 3

E-74

E 2)

E-75

E 2)

E-75

E 2)

E-76

E 2)

OMe

E-76

E 2)

E-77

E 2)

CH 3

E-77

E 2)

E-78

E 2)

CH 3

E-78

E 2)

E-79

E 2)

H/Ph 1)

Ph/H 1)

E-79

E 2)

E-80

E 2)

t-Bu

E-80

E 2)

E-81

E 2)

E-81

E 2)

1) mixture of isomers

Cpd.

R 45

R 44

R 43

R 42

A 11

A 12

A 13

A 14

A 15

A 16

F-1

F-2

F-3

F-4

F-5

F-6

CF 3

F-7

CF 3

F-8

CF 3

F-9

CH 3

F-10

CH 3

F-11

F-12

OMe

F-13

CH 3

F-14

CH 3

F-15

F-16

t-Bu

1) mixture of isomers

Cpd.

R 45

R 44

R 43

R 42

A 24

A 23

A 22

A 21

S-1

A 2)

S-2

A 2)

S-3

A 2)

S-4

A 2)

S-5

A 2)

S-6

A 2)

CF 3

S-7

A 2)

CF 3

S-8

A 2)

CF 3

S-9

A 2)

CH 3

S-10

A 2)

CH 3

S-11

A 2)

S-12

A 2)

OMe

S-13

A 2)

CH 3

S-14

A 2)

CH 3

S-15

A 2)

H/Ph 1)

Ph/H 1)

S-16

A 2)

t-Bu

S-17

B 2)

S-18

B 2)

S-19

B 2)

S-20

B 2)

S-21

B 2)

S-22

B 2)

CF 3

S-23

B 2)

CF 3

S-24

B 2)

CF 3

S-25

B 2)

CH 3

S-26

B 2)

CH 3

S-27

B 2)

S-28

B 2)

OMe

S-29

B 2)

CH 3

S-30

B 2)

CH 3

S-31

B 2)

H/Ph 1)

Ph/

H 1)

S-32

B 2)

t-Bu

S-33

C 2)

S-34

C 2)

S-35

C 2)

S-36

C 2)

S-37

C 2)

S-38

C 2)

CF 3

S-39

C 2)

CF 3

S-40

C 2)

CF 3

S-41

C 2)

CH 3

S-42

C 2)

CH 3

S-43

C 2)

S-44

C 2)

OMe

S-45

C 2)

CH 3

S-46

C 2)

CH 3

S-47

C 2)

H/Ph 1)

Ph/H 1)

S-48

C 2)

t-Bu

S-49

D 2)

S-50

D 2)

S-51

D 2)

S-52

D 2)

S-53

D 2)

S-54

D 2)

CF 3

S-55

D 2)

CF 3

S-56

D 2)

CF 3

S-57

D 2)

CH 3

S-58

D 2)

CH 3

S-59

D 2)

S-60

D 2)

OMe

S-61

D 2)

CH 3

S-62

D 2)

CH 3

S-63

D 2)

H/Ph 1)

Ph/H 1)

S-64

D 2)

t-Bu

S-65

S-66

S-67

S-68

1) mixture of isomers

3) 2,4,4-trimethylpent-2-yl

Cpd.

R 45

R 44

R 43

R 42

A 24

A 23

A 22

A 21

T-1

A 2)

T-2

A 2)

T-3

A 2)

T-4

A 2)

T-5

A 2)

T-6

A 2)

CF 3

T-7

A 2)

CF 3

T-8

A 2)

CF 3

T-9

A 2)

CH 3

T-10

A 2)

CH 3

T-11

A 2)

T-12

A 2)

OMe

T-13

A 2)

CH 3

T-14

A 2)

CH 3

T-15

A 2)

H/Ph 1)

Ph/H 1)

T-16

A 2)

t-Bu

T-17

B 2)

T-18

B 2)

T-19

B 2)

T-20

B 2)

T-21

B 2)

T-22

B 2)

CF 3

T-23

B 2)

CF 3

T-24

B 2)

CF 3

T-25

B 2)

CH 3

T-26

B 2)

CH 3

T-27

B 2)

T-28

B 2)

OMe

T-29

B 2)

CH 3

T-30

B 2)

CH 3

T-31

B 2)

H/Ph 1)

Ph/

H 1)

T-32

B 2)

t-Bu

T-33

C 2)

T-34

C 2)

T-35

C 2)

T-36

C 2)

T-37

C 2)

T-38

C 2)

CF 3

T-39

C 2)

CF 3

T-40

C 2)

CF 3

T-41

C 2)

CH 3

T-42

C 2)

CH 3

T-43

C 2)

T-44

C 2)

OMe

T-45

C 2)

CH 3

T-46

C 2)

CH 3

T-47

C 2)

H/Ph 1)

Ph/H 1)

T-48

C 2)

t-Bu

T-49

D 2)

T-50

D 2)

T-51

D 2)

T-52

D 2)

T-53

D 2)

T-54

D 2)

CF 3

T-55

D 2)

CF 3

T-56

D 2)

CF 3

T-57

D 2)

CH 3

T-58

D 2)

CH 3

T-59

D 2)

T-60

D 2)

OMe

T-61

D 2)

CH 3

T-62

D 2)

CH 3

T-63

D 2)

H/Ph 1)

Ph/H 1)

T-64

D 2)

t-Bu

T-65

T-66

T-67

T-68

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. The device of 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)-[1,11-(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.

Assignments (5)

CORRECTIVE ASSIGNMENT TO CORRECT THE INCORRECT APPL. NO. 14/901,736 PREVIOUSLY RECORDED AT REEL: 039460 FRAME: 0615. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 8, 2017

From: BASF SE

To: UDC IRELAND LIMITED

Reel/Frame 042740/0222 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 25, 2016

From: BASF SE

To: UDC IRELAND LIMITED

Reel/Frame 039460/0615 →

CHANGE OF NAME Recorded Jul 11, 2011

From: CIBA SPECIALTY CHEMICALS CORPORATION

To: CIBA CORPORATION

Reel/Frame 026569/0576 →

ASSET TRANSFER AGREEMENT Recorded Jul 11, 2011