Electroluminiscent metal complexes with dibenzo[f,h] quinoxalines
This invention relates to electroluminescent metal complexes of the formula (I), or (II), 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 the formula
wherein
R 1 , R 2 and R 1′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 1 -C 18 perfluoroalkyl, C 5 -C 12 cycloalkyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, CN,
or —CO—R 28 , or
R 1 and R 2 together form a ring,
R 3 , R 8 , R 3′ and R 8′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, CN, or —CO—R 28 ,
—NR 25 R 26 , —SR 29 , or Si(R 30 ) 3 ,
R 4 , R 7 , R 4′ and R 7′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, CN, or —CO—R 28 ,
—NR 25 R 26 , —SR 29 , or Si(R 30 ) 3 ,
R 5 , R 6 , R 5′ and R 6′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, CN, or —CO—R 28 ,
—NR 25 R 26 , —SR 29 , Si(R 30 ) 3 ,
R 25 and R 26 are independently of each other C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, or
R 25 and R 26 together with the nitrogen atom to which they are bonded form a heteroaromatic ring, or ring system, which may optionally be substituted,
BU is a bridging unit,
D is —CO—; —COO—; —S—; —SO—; —SO 2 —; —O—; —NR 25′ —; —SiR 30 R 31 —; —POR 32 —; —CR 23 ═CR 24 —; or —C≡C—;
E is —OR 29 ; —SR 29 ; —NR 25′ R 26′ ; —COR 28 ; —COOR 27 ; —CONR 25′ R 26′ ; —CN; or halogen; G is E, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by D, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or C 2 -C 18 alkenyl,
R 23 , R 24 , R 25′ and R 26′ are independently of each other H; 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—;
R 27 and R 28 are independently of each other H; 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—,
R 29 is H; 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—,
R 30 and R 31 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and
R 32 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl,
M is Pd, Rh, Re, Pt, or Ir,
L is a mono-, or bi-dentate ligand,
if L is a monodentate ligand,
m is 0, or 2, and n is 1, or 2, if M is Pd, or Pt,
m is 0, 2, or 4, and n is 1, 2, or 3, if M is Rh, Ir or Re,
if L is a bidentate ligand,
m is 0, or 1, and n is 1, or 2, if M is Pd, or Pt,
m is 0, 1, or 2, and n is 1, 2, or 3, if M is Rh, Ir or Re,
with the proviso that at least one of R 1 , R 2 , R 3 , R 8 , R 4 , R 7 , R 5 and R 6 is different from H and the further proviso that
are excluded; and with the further proviso that organometallic complexes having a structure represented by the general formula
are excluded,
wherein Ar represents an aryl group having 6 to 25 carbon atoms;
A 1 represents any one of hydrogen, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms;
A 2 to A 8 each represent any one of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen group;
M 10 represents a metal of Group 9 elements and Group 10 elements;
L 10 represents a monoanionic ligand; and
u is 2 when the metal is a Group 9 element, and u is 1 when the metal is a Group 10 element.
2. The compound of the formula I, or II according to claim 1 , wherein
R 1 , R 1′ and R 2 are independently of each other H, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G,
or CN, or
R 1 and R 2 together form a group
R 206′ , R 208′ , R 205 , R 206 , R 207 , R 208 , R 209 and R 210 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy;
R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 and R 308 are independently of each other H, or C 1 -C 18 alkyl, R 3 , R 8 , R 3′ and R 8′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by —O—, C 7 -C 25 arylalkyl, CN, or —NR 25 R 26 ;
R 4 , R 7 , R 4 and R 7 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by —O—, C 7 -C 25 arylalkyl, CN, —NR 25 R 26 ;
R 5 , R 6 , R 5′ and R 6′ are H,
R 25 and R 26 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 25 and R 26 together with the nitrogen atom to which they are bonded form a heteroaromatic ring system
m′ is 0, 1, or 2;
m″ can be the same or different at each occurence and is 0, 1, 2, or 3;
R 41 can be the same or different at each occurence and is Cl, F, CN, N(R 45 ) 2 , a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, a C 1 -C 25 alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by —NR 45 —, —O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 41 , or
two or more groups R 41 form a ring system;
R 45 is H, a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by —NR 45″ —, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 41 , and
R 45″ is H, a C 1 -C 25 alkyl group, or a C 4 -C 18 cycloalkyl group,
E is —OR 29 ; —SR 29 ; —NR 25′ R 26′ , CN, or F; G is E, CF 3 , C 1 -C 18 alkyl, or C 2 -C 18 alkenyl,
M is Pd, Rh, Re, Pt, or Ir,
L is a bidentate ligand,
m is 0, or 1, and n is 1, or 2, if M is Pd, or Pt,
m is 0, 1, or 2, and n is 1, 2, or 3, if M is Rh, Ir or Re, and
R 29 ; R 29 ; R 25′ and R 26′ are as defined in claim 1 ,
with the proviso that at least one of R 3 , R 8 , R 4 and R 7 is different from H.
3. The compound of the formula I according to claim 1 , wherein at least one of the substituents R 1 , R 4 and R 7 is a group —NR 25 R 26 , or C 6 -C 24 aryl, which is substituted by —NR 25 R 26 , wherein R 25 and R 26 are independently of each other
wherein R 116 and R 117 are independently of each other C 1 -C 25 alkyl, which may optionally be interrupted by —O—, or C 1 -C 25 alkoxy; or R 25 and R 26 together with the nitrogen atom to which they are bonded form a group of formula
R 41 is H, or C 1 -C 25 alkyl.
4. The compound of claim 1 having a structure (Va), (Vb), (Vc), (VIa), (VIb), or (VIc) below:
wherein
R 1 , R 1′ and R 2 are independently of each other H, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, or CN,
R 3 , R 8 , R 3′ and R 8′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by —O—, C 7 -C 25 arylalkyl, CN, or —NR 25 R 26 ;
R 4 , R 7 , R 4′ and R 7′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by —O—, C 7 -C 25 arylalkyl, CN, —NR 25 R 26 ;
R 25 and R 26 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 25 and R 26 together with the nitrogen atom to which they are bonded form a heteroaromatic ring system
m′ is 0, 1, or 2;
m″ can be the same or different at each occurence and is 0, 1, 2, or 3;
R 41 can be the same or different at each occurence and is Cl, F, CN, N(R 45 ) 2 , a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, a C 1 -C 25 alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by —NR 45 —, —O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 41 , or
two or more groups R 41 form a ring system;
R 45 is H, a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, in which one or more carbon atoms which are not in neighbourhood to each other can be replaced by —NR 45″ —, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 41 , and
R 45″ is H, a C 1 -C 25 alkyl group, or a C 4 -C 18 cycloalkyl group,
E is —OR 29 ; —SR 29 ; —NR 25′ R 26′ , CN or F; G is E, C 1 -C 18 alkyl, CF 3 , or C 2 -C 18 alkenyl,
R 29 ; R 29 ; R 25′ and R 26′ are as defined in claim 1 ,
M 2 is Rh, Re or Ir,
L is a bidentate ligand, and
L′″ is a monodentate ligand, or
a compound of claim 1 having a structure (VIIa), (VIIb), (VIIIa), or (VIIIb) below:
wherein M 4 is Pd, or Pt, and L, R 1 , R 2 , R 1′ , R 3 , R 4 , R 3′ , R 4′ , R 7 , R 8 , R 7′ and R 8′ are as defined above.
5. The compound of formula I according to claim 1 , wherein
R 2 is H, or CH 3 ,
R 1 and R 1′ are H, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G,
or CN,
R 3 , R 8 , R 3′ and R 8′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 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 alkoxy which are interrupted by —O—; C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is interrupted by —O—; or —NR 25 R 26 ;
R 4 , R 7 , R 4 and R 7 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 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 alkoxy which are interrupted by —O—; C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is interrupted by —O—; or —NR 25 R 26 ;
R 25 and R 26 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 alkoxy which are interrupted by —O—; or
R 25 and R 26 together with the nitrogen atom to which they are bonded form a heteroaromatic ring system
wherein R 41 is H, or C 1 -C 25 alkyl;
M 2 is Ir, and
M 4 is Pd or Pt, and
L is a bidentate ligand.
6. The compound of 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 group of formula
wherein R 211 , R 212 , R 213 , and R 214 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; the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group, and alkyloxycarbonyl group represented by R 211 , R 212 , R 213 , and R 214 may be substituted; or R 213 and R 214 or R 212 and R 213 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′26′ , or —COOR 27′ , or C 2 -C 10 heteroaryl; wherein
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—;
R 305 is C 1 -C 18 alkyl, or C 6 -C 18 aryl, and
R 306 is C 1 -C 18 alkyl, or C 6 -C 18 aryl; or L is a bidentate ligand L′ 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, C 6 -C 18 aryl, 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, or C 1 -C 8 perfluoroalkyl,
R 20 is hydrogen, 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,
R 22 and R 23 are independently of each other C q (H+F) 2q+1 , or C 6 (H+F) 5 , R 24 can be the same or different at each occurrence and is selected from H, or C q (H+F) 2q+1 ,
R 46 is C 1 -C 8 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 8 alkyl,
q is an integer of 1 to 24, p is 2, or 3, or L is a bidentate ligand L″ selected from
7. The compound of claims 6 :
Cpd.
L
R 1
R 2
R 3 and R 8
R 4 and R 7
A-1
A 1)
—CH 3
H
H
A-2
A 1)
—CH 3
H
H
A-3
A 1)
—CH 3
H
H
A-4
A 1)
—CH 3
H
H
A-5
A 1)
—CH 3
H
H
A-6
A 1)
—CH 3
H
H
A-7
A 1)
—CH 3
H
H
A-8
A 1)
—CH 3
H
H
A-9
A 1)
—CH 3
H
H
A-10
A 1)
—CH 3
H
H
A-11
A 1)
—CH 3
H
H
A-12
A 1)
—CH 3
H
H
A-13
A 1)
—CH 3
H
H
A-14
A 1)
—CH 3
H
H
A-15
A 1)
—CH 3
H
H
A-16
A 1)
—CH 3
H
H
A-17
A 1)
—CH 3
H
H
A-18
A 1)
—CH 3
H
H
A-19
A 1)
H
H
H
A-20
A 1)
H
H
H
A-21
A 1)
H
H
H
A-22
A 1)
H
H
H
A-23
A 1)
H
H
H
A-24
A 1)
H
H
H
A-25
A 1)
H
H
H
A-26
A 1)
H
H
H
A-27
A 1)
H
H
H
A-28
A 1)
H
H
H
A-29
A 1)
H
H
H
A-30
A 1)
H
H
H
A-31
A 1)
H
H
H
A-32
A 1)
H
H
H
A-33
A 1)
H
H
H
A-34
A 1)
H
H
H
A-35
A 1)
H
H
H
A-36
A 1)
H
H
H
A-37
A 1)
Ph
H
H
A-38
A 1)
Ph
H
H
A-39
A 1)
Ph
H
H
A-40
A 1)
Ph
H
H
A-41
A 1)
Ph
H
H
A-42
A 1)
Ph
H
H
A-43
A 1)
Ph
H
H
A-44
A 1)
Ph
H
H
A-45
A 1)
Ph
H
H
A-46
A 1)
Ph
H
H
A-47
A 1)
Ph
H
H
A-48
A 1)
Ph
H
H
A-49
A 1)
Ph
H
H
A-50
A 1)
Ph
H
H
A-51
A 1)
Ph
H
H
A-52
A 1)
Ph
H
H
A-53
A 1)
Ph
H
H
A-54
A 1)
Ph
H
H
A-55
A 1)
H
H
A-56
A 1)
H
H
A-57
A 1)
H
H
A-58
A 1)
H
H
A-59
A 1)
H
H
A-60
A 1)
H
H
A-61
A 1)
H
H
A-62
A 1)
H
H
A-63
A 1)
H
H
A-64
A 1)
H
H
A-65
A 1)
H
H
A-66
A 1)
H
H
A-67
A 1)
H
H
A-68
A 1)
H
H
A-69
A 1)
H
H
A-70
A 1)
H
H
A-71
A 1)
H
H
A-72
A 1)
H
H
A-73
A 1)
H
H
A-74
A 1)
H
H
A-75
A 1)
H
H
A-76
A 1)
H
H
A-77
A 1)
H
H
A-78
A 1)
H
H
A-79
A 1)
H
H
A-80
A 1)
H
H
A-81
A 1)
H
H
A-82
A 1)
H
H
A-83
A 1)
H
H
A-84
A 1)
H
H
A-85
A 1)
H
H
A-86
A 1)
H
H
A-87
A 1)
H
H
A-88
A 1)
H
H
A-89
A 1)
H
H
A-90
A 1)
H
H
A-91
A 1)
H
H
A-92
A 1)
H
H
A-93
A 1)
H
H
A-94
A 1)
H
H
A-95
A 1)
H
H
A-96
A 1)
H
H
A-97
A 1)
H
H
A-98
A 1)
H
H
A-99
A 1)
H
H
A-100
A 1)
H
H
A-101
A 1)
H
H
A-102
A 1)
H
H
A-103
A 1)
H
H
A-104
A 1)
H
H
A-105
A 1)
H
H
A-106
A 1)
H
H
A-107
A 1)
H
H
A-108
A 1)
H
H
A-109
A 1)
H
H
A-110
A 1)
H
H
A-111
A 1)
H
H
A-112
A 1)
H
H
A-113
A 1)
H
H
A-114
A 1)
H
H
A-115
A 1)
H
H
A-116
A 1)
H
H
A-117
A 1)
H
H
A-118
A 1)
H
H
A-119
A 1)
H
H
A-120
A 1)
H
H
A-121
A 1)
H
H
A-122
A 1)
H
H
A-123
A 1)
H
H
A-124
A 1)
H
H
A-125
A 1)
H
H
A-126
A 1)
H
H
A-127
A 1)
H
H
A-128
A 1)
H
H
A-129
A 1)
H
H
A-130
A 1)
H
H
A-131
A 1)
H
H
A-132
A 1)
H
H
A-133
A 1)
H
H
A-134
A 1)
H
H
A-135
A 1)
H
H
A-136
A 1)
H
H
A-137
A 1)
H
H
A-138
A 1)
H
H
A-139
A 1)
H
H
A-140
A 1)
H
H
A-141
A 1)
H
H
A-142
A 1)
H
H
A-143
A 1)
H
H
A-144
A 1)
H
H
A-145
A 1)
H
H
A-146
A 1)
H
H
A-147
A 1)
H
H
A-148
A 1)
H
H
A-149
A 1)
H
H
A-150
A 1)
H
H
A-151
A 1)
H
H
H
A-152
A 1)
H
H
H
A-153
A 1)
H
H
H
A-154
A 1)
H
H
H
A-155
A 1)
H
H
H
A-156
A 1)
CH 3
H
A-157
A 1)
H
H
H
A-158
A 1)
H
H
H
A-159
A 1)
H
H
H
A-160
A 1)
H
H
H
A-161
A 1)
H
H
H
A-162
A 1)
CH 3
H
H
A-163
A 1)
2-ethylhexyl
H
H
H
A-164
A 1)
n-butyl
H
H
H
A-165
A 1)
tert-butyl
H
H
H
A-166
A 1)
—(CH 2 ) 4 —
H
H
A-167
A 1)
2-ethylhexyl
CH 3
H
H
A-168
A 1)
n-butyl
CH 3
H
H
A-169
A 1)
tert-butyl
CH 3
H
H
A-170
A 1)
2-ethylhexyl
H
H
propyl
A-171
A 1)
n-butyl
H
H
propyl
A-172
A 1)
tert-butyl
H
H
propyl
A-173
A 1)
—(CH 2 ) 4 —
—(CH 2 ) 4 —
H
propyl
A-174
A 1)
2-ethylhexyl
CH 3
H
propyl
A-175
A 1)
n-butyl
CH 3
H
propyl
A-176
A 1)
tert-butyl
CH 3
H
propyl
B-1
B 1)
—CH 3
H
H
B-2
B 1)
—CH 3
H
H
B-3
B 1)
—CH 3
H
H
B-4
B 1)
—CH 3
H
H
B-5
B 1)
—CH 3
H
H
B-6
B 1)
—CH 3
H
H
B-7
B 1)
—CH 3
H
H
B-8
B 1)
—CH 3
H
H
B-9
B 1)
—CH 3
H
H
B-10
B 1)
—CH 3
H
H
B-11
B 1)
—CH 3
H
H
B-12
B 1)
—CH 3
H
H
B-13
B 1)
—CH 3
H
H
B-14
B 1)
—CH 3
H
H
B-15
B 1)
—CH 3
H
H
B-16
B 1)
—CH 3
H
H
B-17
B 1)
—CH 3
H
H
B-18
B 1)
—CH 3
H
H
B-19
B 1)
H
H
H
B-20
B 1)
H
H
H
B-21
B 1)
H
H
H
B-22
B 1)
H
H
H
B-23
B 1)
H
H
H
B-24
B 1)
H
H
H
B-25
B 1)
H
H
H
B-26
B 1)
H
H
H
B-27
B 1)
H
H
H
B-28
B 1)
H
H
H
B-29
B 1)
H
H
H
B-30
B 1)
H
H
H
B-31
B 1)
H
H
H
B-32
B 1)
H
H
H
B-33
B 1)
H
H
H
B-34
B 1)
H
H
H
B-35
B 1)
H
H
H
B-36
B 1)
H
H
H
B-37
B 1)
Ph
H
H
B-38
B 1)
Ph
H
H
B-39
B 1)
Ph
H
H
B-40
B 1)
Ph
H
H
B-41
B 1)
Ph
H
H
B-42
B 1)
Ph
H
H
B-43
B 1)
Ph
H
H
B-44
B 1)
Ph
H
H
B-45
B 1)
Ph
H
H
B-46
B 1)
Ph
H
H
B-47
B 1)
Ph
H
H
B-48
B 1)
Ph
H
H
B-49
B 1)
Ph
H
H
B-50
B 1)
Ph
H
H
B-51
B 1)
Ph
H
H
B-52
B 1)
Ph
H
H
B-53
B 1)
Ph
H
H
B-54
B 1)
Ph
H
H
B-55
B 1)
H
H
B-56
B 1)
H
H
B-57
B 1)
H
H
B-58
B 1)
H
H
B-59
B 1)
H
H
B-60
B 1)
H
H
B-61
B 1)
H
H
B-62
B 1)
H
H
B-63
B 1)
H
H
B-64
B 1)
H
H
B-65
B 1)
H
H
B-66
B 1)
H
H
B-67
B 1)
H
H
B-68
B 1)
H
H
B-69
B 1)
H
H
B-70
B 1)
H
H
B-71
B 1)
H
H
B-72
B 1)
H
H
B-73
B 1)
H
H
B-74
B 1)
H
H
B-75
B 1)
H
H
B-76
B 1)
H
H
B-77
B 1)
H
H
B-78
B 1)
H
H
B-79
B 1)
H
H
B-80
B 1)
H
H
B-81
B 1)
H
H
B-82
B 1)
H
H
B-83
B 1)
H
H
B-84
B 1)
H
H
B-85
B 1)
H
H
B-86
B 1)
H
H
B-87
B 1)
H
H
B-88
B 1)
H
H
B-89
B 1)
H
H
B-90
B 1)
H
H
B-91
B 1)
H
H
B-92
B 1)
H
H
B-93
B 1)
H
H
B-94
B 1)
H
H
B-95
B 1)
H
H
B-96
B 1)
H
H
B-97
B 1)
H
H
B-98
B 1)
H
H
B-99
B 1)
H
H
B-100
B 1)
H
H
B-101
B 1)
H
H
B-102
B 1)
H
H
B-103
B 1)
H
H
B-104
B 1)
H
H
B-105
B 1)
H
H
B-106
B 1)
H
H
B-107
B 1)
H
H
B-108
B 1)
H
H
B-109
B 1)
H
H
B-110
B 1)
H
H
B-111
B 1)
H
H
B-112
B 1)
H
H
B-113
B 1)
H
H
B-114
B 1)
H
H
B-115
B 1)
H
H
B-116
B 1)
H
H
B-117
B 1)
H
H
B-118
B 1)
H
H
B-119
B 1)
H
H
B-120
B 1)
H
H
B-121
B 1)
H
H
B-122
B 1)
H
H
B-123
B 1)
H
H
B-124
B 1)
H
H
B-125
B 1)
H
H
B-126
B 1)
H
H
B-127
B 1)
H
H
B-128
B 1)
H
H
B-129
B 1)
H
H
B-130
B 1)
H
H
B-131
B 1)
H
H
B-132
B 1)
H
H
B-133
B 1)
H
H
B-134
B 1)
H
H
B-135
B 1)
H
H
B-136
B 1)
H
H
B-137
B 1)
H
H
B-138
B 1)
H
H
B-139
B 1)
H
H
B-140
B 1)
H
H
B-141
B 1)
H
H
B-142
B 1)
H
H
B-143
B 1)
H
H
B-144
B 1)
H
H
B-145
B 1)
H
H
B-146
B 1)
H
H
B-147
B 1)
H
H
B-148
B 1)
H
H
B-149
B 1)
H
H
B-150
B 1)
H
H
B-151
B 1)
H
H
H
B-152
B 1)
H
H
H
B-153
B 1)
H
H
H
B-154
B 1)
H
H
H
B-155
B 1)
H
H
H
B-156
B 1)
CH 3
H
B-157
B 1)
H
H
H
B-158
B 1)
H
H
H
B-159
B 1)
H
H
H
B-160
B 1)
H
H
H
B-161
B 1)
H
H
H
B-162
B 1)
CH 3
H
H
B-163
B 1)
2-ethylhexyl
H
H
H
B-164
B 1)
n-butyl
H
H
H
B-165
B 1)
tert-butyl
H
H
H
B-166
B 1)
—(CH 2 ) 4 —
H
H
H
B-167
B 1)
2-ethylhexyl
CH 3
H
H
B-168
B 1)
n-butyl
CH 3
H
H
B-169
B 1)
tert-butyl
CH 3
H
H
B-170
B 1)
2-ethylhexyl
H
H
propyl
B-171
B 1)
n-butyl
H
H
propyl
B-172
B 1)
tert-butyl
H
H
propyl
B-171
B 1)
—(CH 2 ) 4 —
H
H
propyl
B-174
B 1)
2-ethylhexyl
CH 3
H
propyl
B-175
B 1)
n-butyl
CH 3
H
propyl
B-176
B 1)
tert-butyl
CH 3
H
propyl
1) A =
B =
L a is
or
Cpd.
L
R 1
R 2
R 7 = R 42)
C-1
A 1)
—CH 3
H
C-2
A 1)
—CH 3
H
C-3
A 1)
—CH 3
H
C-4
A 1)
—CH 3
H
C-5
A 1)
—CH 3
H
C-6
A 1)
—CH 3
H
C-7
A 1)
—CH 3
H
C-8
A 1)
—CH 3
H
C-9
A 1)
—CH 3
H
C-10
A 1)
H
H
C-12
A 1)
H
H
C-13
A 1)
H
H
C-14
A 1)
H
H
C-15
A 1)
H
H
C-16
A 1)
H
H
C-17
A 1)
H
H
C-18
A 1)
H
H
C-19
A 1)
H
H
C-20
A 1)
Ph
H
C-21
A 1)
Ph
H
C-22
A 1)
Ph
H
C-23
A 1)
Ph
H
C-24
A 1)
Ph
H
C-25
A 1)
Ph
H
C-26
A 1)
Ph
H
C-27
A 1)
Ph
H
C-28
A 1)
Ph
H
C-29
A 1)
H
C-30
A 1)
H
C-31
A 1)
H
C-32
A 1)
H
C-33
A 1)
H
C-34
A 1)
H
C-35
A 1)
H
C-36
A 1)
H
C-37
A 1)
H
C-38
A 1)
H
C-39
A 1)
H
C-40
A 1)
H
C-41
A 1)
H
C-42
A 1)
H
C-43
A 1)
H
C-44
A 1)
H
C-45
A 1)
H
C-46
A 1)
H
C-47
A 1)
H
C-48
A 1)
H
C-49
A 1)
H
C-50
A 1)
H
C-51
A 1)
H
C-52
A 1)
H
C-53
A 1)
H
C-54
A 1)
H
C-55
A 1)
H
C-56
A 1)
H
C-57
A 1)
H
C-58
A 1)
H
C-59
A 1)
H
C-60
A 1)
H
C-61
A 1)
H
C-62
A 1)
H
C-63
A 1)
H
C-64
A 1)
H
C-65
A 1)
H
C-66
A 1)
H
C-67
A 1)
H
C-68
A 1)
H
C-69
A 1)
H
C-70
A 1)
H
C-71
A 1)
H
C-72
A 1)
H
C-73
A 1)
H
C-74
A 1)
H
C-76
A 1)
H
C-78
A 1)
H
C-79
A 1)
H
C-80
A 1)
H
H
C-81
A 1)
CH 3
H
C-82
A 1)
2-ethylhexyl
H
H
C-83
A 1)
n-butyl
H
H
C-84
A 1)
tert-butyl
H
H
C-85
A 1)
—(CH 2 ) 4 —
H
H
C-86
A 1)
2-ethylhexyl
CH 3
H
C-87
A 1)
n-butyl
CH 3
H
C-88
A 1)
tert-butyl
CH 3
H
C-89
A 1)
2-ethylhexyl
H
propyl
C-90
A 1)
n-butyl
H
propyl
C-91
A 1)
tert-butyl
H
propyl
C-92
A 1)
—(CH 2 ) 4 —
H
propyl
C-93
A 1)
2-ethylhexyl
CH 3
propyl
C-94
A 1)
n-butyl
CH 3
propyl
C-95
A 1)
tert-butyl
CH 3
propyl
D-1
B 1)
—CH 3
H
D-2
B 1)
—CH 3
H
D-3
B 1)
—CH 3
H
D-4
B 1)
—CH 3
H
D-5
B 1)
—CH 3
H
D-6
B 1)
—CH 3
H
D-7
B 1)
—CH 3
H
D-8
B 1)
—CH 3
H
D-9
B 1)
—CH 3
H
D-10
B 1)
H
H
D-12
B 1)
H
H
D-13
B 1)
H
H
D-14
B 1)
H
H
D-15
B 1)
H
H
D-16
B 1)
H
H
D-17
B 1)
H
H
D-18
B 1)
H
H
D-19
B 1)
H
H
D-20
B 1)
Ph
H
D-21
B 1)
Ph
H
D-22
B 1)
Ph
H
D-23
B 1)
Ph
H
D-24
B 1)
Ph
H
D-25
B 1)
Ph
H
D-26
B 1)
Ph
H
D-27
B 1)
Ph
H
D-28
B 1)
Ph
H
D-29
B 1)
H
D-30
B 1)
H
D-31
B 1)
H
D-32
B 1)
H
D-33
B 1)
H
D-34
B 1)
H
D-35
B 1)
H
D-36
B 1)
H
D-37
B 1)
H
D-38
B 1)
H
D-39
B 1)
H
D-40
B 1)
H
D-41
B 1)
H
D-42
B 1)
H
D-43
B 1)
H
D-44
B 1)
H
D-45
B 1)
H
D-46
B 1)
H
D-47
B 1)
H
D-48
B 1)
H
D-49
B 1)
H
D-50
B 1)
H
D-51
B 1)
H
D-52
B 1)
H
D-53
B 1)
H
D-54
B 1)
H
D-55
B 1)
H
D-56
B 1)
H
D-57
B 1)
H
D-58
B 1)
H
D-59
B 1)
H
D-60
B 1)
H
D-61
B 1)
H
D-62
B 1)
H
D-63
B 1)
H
D-64
B 1)
H
D-65
B 1)
H
D-66
B 1)
H
D-67
B 1)
H
D-68
B 1)
H
D-69
B 1)
H
D-70
B 1)
H
D-71
B 1)
H
D-72
B 1)
H
D-73
B 1)
H
D-74
B 1)
H
D-76
B 1)
H
D-78
B 1)
H
D-79
B 1)
H
D-80
B 1)
H
H
D-81
B 1)
CH 3
H
D-82
B 1)
2-ethylhexyl
H
H
D-83
B 1)
n-butyl
H
H
D-84
B 1)
tert-butyl
H
H
D-85
B 1)
—(CH 2 ) 4 —
H
H
D-86
B 1)
2-ethylhexyl
CH 3
H
D-87
B 1)
n-butyl
CH 3
H
D-88
B 1)
tert-butyl
CH 3
H
D-89
B 1)
2-ethylhexyl
H
propyl
D-90
B 1)
n-butyl
H
propyl
D-91
B 1)
tert-butyl
H
propyl
D-92
B 1)
—(CH 2 ) 4 —
H
propyl
D-93
B 1)
2-ethylhexyl
CH 3
propyl
D-94
B 1)
n-butyl
CH 3
propyl
D-95
B 1)
tert-butyl
CH 3
propyl
2) The ligand L a used for the production of comp. C-1 (etc.) is present in form of two isomers:
Cpd.
R 1
R 2
R 4
R 7
E-1
H
H
H
E-2
H
H
H
E-3
H
H
H
E-4
H
H
H
E-5
H
H
H
E-6
H
H
H
E-7
H
H
H
E-8
H
H
H
E-9
H
H
H
E-10
H
H
E-11
H
H
E-12
H
H
E-13
H
H
E-14
H
H
E-15
H
H
E-16
H
H
E-17
H
H
E-18
H
H
E-19
H
H
E-20
H
H
E-21
H
H
E-22
H
H
E-23
H
H
E-24
H
H
E-25
H
H
E-26
H
H
E-27
H
H
E-28
H
H
E-29
H
H
E-30
H
H
E-31
H
H
E-32
H
H
E-33
H
H
E-34
H
H
E-35
H
H
E-36
H
H.
8. The compound of the formula I according to claim 1 , which is a compound of formula
wherein M 2 is iridium, R 1 is H, cyclohexyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups, C 1 -C 18 alkyl,
wherein
n 3 is 0, or an integer 1, 2, 3, 4, or 5, or 5, R 11 can be same, or different in each occurrence and is C 1 -C 25 alkyl, C 1 -C 25 alkoxy, —NR 25 R 26 , F, or CF 3 ,
R 4 and R 7 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 1 -C 18 alkoxy, which may be interrupted by —O—, or —NR 25 R 26 ;
R 25 and R 26 are independently of each other
R 116 and R 117 are independently of each other C 1 -C 25 alkyl, which may optionally be interrupted by —O—, or C 1 -C 25 alkoxy; or R 25 and R 26 together with the nitrogen atom to which they are bonded form a group of formula
R 41 is H, or C 1 -C 25 alkyl, and
L is as defined in claim 1 .
9. The compound of the formula I according to claim 1 , which is a compound of formula
formula LIr(L a ) 2 , or Ir(L a ) 3 , wherein L a is a group of formula
wherein R 1 is H, C 1 -C 18 alkyl, cyclohexyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups,
wherein n 3 is 0, or an integer 1, 2, 3, 4, or 5, R 11 can be same, or different in each occurrence and is C 1 -C 25 alkyl, C 1 -C 25 alkoxy, —NR 25 R 26 , F, or CF 3 ,
R 2 is H, or CH 3 ,
R 4 and R 7 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by —NR 25 R 26 , C 1 -C 18 alkoxy which may be interrupted by —O—, or —NR 25 R 26 ;
R 25 and R 26 are independently of each other
R 116 and R 117 are independently of each other C 1 -C 25 alkyl, which may optionally be interrupted by —O—, or C 1 -C 25 alkoxy; or R 25 and R 26 together with the nitrogen atom to which they are bonded form a group of formula
R 41 is H, or C 1 -C 25 alkyl, and
L is as defined in claim 1 .
10. The compound of the formula I according to claim 1 , which is a compound of formula
wherein R 1 is C 2 -C 10 alkyl, cyclohexyl, which can optionally be substituted by one to three C 1 -C 4 alkyl groups, R 2 is H, or CH 3 , and L is
11. An organic electronic device, comprising an emitting layer wherein the emitting layer comprises a compound according to claim 1 .
12. The device of claim 11 , 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), N,N′-di-α-naphthyl-N,N′-diphenyl-4,4′-diphenyldiamine (α-NPD), porphyrinic compounds, and combinations thereof, or electrontransporting materials, selected from tris(8-hydroxyquinolato)aluminium (Alq3), bis(2-methyl-8-hydroxyquinaolato)(p-phenylphenolato)aluminium (BAlq), tetrakis(8-hydroxyquinolato)zirconium (ZrQ) and mixtures thereof.
13. An electronic device comprising a compound according to claim 1 which electronic device is a organic light emitting diodes (OLEDs), as oxygen sensitive indicators, as phosphorescent indicators in bioassays, or catalysts.
14. Compounds of formula
wherein X is H, methyl, or ethyl, and L a is
wherein R 1 , R 2 , R 1′ , R 3 , R 4 , R 3′ , R 4′ , R 5 , R 6 , R 5′ , R 6′ , R 7 , R 8 , R 7′ and R 8′ are as defined in claim 1 , with the proviso that at least one of R 1 , R 2 , R 3 , R 8 , R 4 , R 7 , R 5 and R 6 is different from H and the further proviso that a compound of formula
wherein L a is
a compound of formula
wherein L a is
and a compound of formula
wherein L a is
are excluded.