High-molecular copolymer containing metal coordination compound and organic electroluminescence element using the same

• US 20060287498A1
• Filed: 06/18/2004
• Published: 12/21/2006
• Est. Priority Date: 06/18/2003
• Status: Active Grant

• Current Assignee: Hitachi Chemical Company Limited (Resonac Holdings Corp.)
• Original Assignee: Hitachi Chemical Company Limited (Resonac Holdings Corp.)
• Inventors: Morishita, Yoshii, Tsuda, Yoshihiro, Nomura, Satoyuki
• Granted Patent: US 8,008,418 B2
• Time in Patent Office: Days
• US Class Current: 528/422
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1416 Condensed systems
• CPC Class Codes: C09K 2211/1466 containing nitrogen as the only heteroatom
• CPC Class Codes: C09K 2211/185 of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• CPC Class Codes: H10K 2101/10 Triplet emission
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/321 Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
• CPC Class Codes: H10K 85/341 Transition metal complexes, e.g. Ru(II)polypyridine complexes H10K85/331 takes precedence
• CPC Class Codes: H10K 85/342 comprising iridium
• CPC Class Codes: H10K 85/6565 Oxadiazole compounds

Abstract

It is an object of the present invention to provide a copolymer containing a metal coordination compound that has blue phosphorescence emission with excellent color purity and, furthermore, to provide a copolymer containing a metal coordination compound that has luminescence of various colors from blue to red and a long operating life. The present invention relates to a metal coordination compound-containing copolymer that contains a metal coordination compound monomer unit represented by any one of Formulae (1) to (12): and at least one type of monomer unit selected from the group consisting of a substituted or unsubstituted quinoline monomer unit, a substituted or unsubstituted arylene and/or heteroarylene monomer unit, a substituted or unsubstituted branched monomer unit, and a substituted or unsubstituted conjugated monomer unit.

Claims

1. A metal coordination compound-containing copolymer comprising:

a metal coordination compound monomer unit represented by any one of Formulae (1) to (12),

(in the formulae, M is Ir, Rh, Ru, Os, Pd, or Pt, and n is 1 or 2;

ring A is a cyclic compound containing a nitrogen atom bonded to M;

X₁ to X₇ and R are independently substituents selected from the group consisting of —

R¹, —

OR², —

SR³, —

OCOR⁴, —

COOR⁵, —

SiR⁶R⁷R⁸, and —

NR⁹R¹⁰ (here, R¹ to R¹⁰ are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1 to C22 straight-chain, cyclic, or branched alkyl group or a corresponding halogen-substituted alkyl group in which a part or all of the hydrogen atoms are substituted by a halogen atom, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a C7 to C30 aralkyl group, or a corresponding halogen-substituted aryl group, halogen-substituted heteroaryl group, or halogen-substituted aralkyl group, in which a part or all of the hydrogen atoms are substituted by a halogen atom, and R¹ to R¹⁰ may be identical to or different from each other), X₁ to X₇ may be identical to or different from each other, and ring A may have a substituent that is the same as the groups defined by X₁ to X₇;

ring C is a compound that is bonded to M and that bonds to a linking group; and

ring C may have a substituent that is the same as the groups defined by X₁ to X₇); and

at least one type of monomer unit selected from the group consisting of a substituted or unsubstituted quinoline monomer unit, a substituted or unsubstituted arylene and/or heteroarylene monomer unit, a substituted or unsubstituted branched monomer unit, and a substituted or unsubstituted conjugated monomer unit.

2. The metal coordination compound-containing copolymer according to claim 1, wherein the copolymer comprises

a metal coordination compound monomer unit represented by any one of the Formulae (1) to (12),

a substituted or unsubstituted quinoline monomer unit represented by Formulae (13-1),

(in the formulae, a plurality of V are independently substituents selected from the group consisting of —

R¹, —

OR², —

SR³, —

OCOR⁴, —

COOR⁵, and —

SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), may be identical to or different from each other, and are bonded to a substitutable position of a quinoline residue, and each a is independently an integer of 0 to 3;

D is selected from the group consisting of a single bond and arylene; and

E is a divalent linking group selected from the group consisting of a single bond, —

O—

, —

S—

, —

C(O)—

, —

S(O)—

, —

S(O₂)—

, —

W—

, —

(—

O—

W—

)m-O—

(m is an integer of 1 to

     3), and -Q- [in the formulae, W is a divalent group selected from the group consisting of —

Ra—

, —

Ar′

—

, —

Ra—

Ar′

—

, —

Ra′

—

O—

Ra′

—

, —

Ra′

—

C(O)O—

Ra′

—

, —

Ra′

—

NHCO—

Ra′

—

, —

Ra—

C(O)—

Ra—

, —

Ar′

—

C(O)—

Ar′

—

, -Het′

-, —

Ar′

—

S—

Ar′

—

, —

Ar′

—

S(O)—

Ar′

—

, —

Ar′

—

S(O₂)—

Ar′

—

, and —

Ar′

-Q-Ar′

—

;

Ra is alkylene, Ar′

is arylene, each Ra′

is independently a group selected from the group consisting of alkylene, arylene, and a mixed alkylene/arylene group, Het′

is heteroarylene, and Q is a divalent group containing a quaternary carbon]), and

a substituted or unsubstituted arylene and/or heteroarylene monomer unit,

the monomer units each being bonded via a linking group represented by Formula (14),

-(G)b- 

 

(14)

(in the formula, G is a divalent group selected from the group consisting of —

O—

, —

R—

O—

R—

, —

S—

, —

NR—

, —

CR₂—

, —

SiR₂—

, —

SiR₂—

O—

SiR₂—

, and —

SiR₂—

O—

SiR₂—

O—

SiR₂—

(here, R is a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b is an integer of 0 or

     1).

3. The metal coordination compound-containing copolymer according to claim 1, wherein the copolymer comprises

a metal coordination compound monomer unit represented by any one of the Formulae (1) to (12),

a substituted or unsubstituted quinoline monomer unit represented by Formulae (13-1),

(in the formulae, a plurality of V are independently substituents selected from the group consisting of —

R¹, —

OR², —

SR³, —

OCOR⁴, —

COOR⁵, and —

SiR⁶R⁷R⁸ (here, R′

to R⁸ are a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), may be identical to or different from each other, and are bonded to a substitutable position of a quinoline residue, and each a is independently an integer of 0 to 3;

D is selected from the group consisting of a single bond and arylene; and

E is a divalent linking group selected from the group consisting of a single bond, —

O—

, —

S—

, —

C(O)—

, —

S(O)—

, —

S(O₂)—

, —

W—

, —

(—

O—

W—

)m-O—

(m is an integer of 1 to

     3), and -Q- [in the formulae, W is a divalent group selected from the group consisting of —

Ra—

, —

Ar′

—

, —

Ra—

Ar′

—

, —

Ra′

—

O—

Ra′

—

, —

Ra′

—

C(O)O—

Ra′

—

, —

Ra′

—

NHCO—

Ra′

—

, —

Ra—

C(O)—

Ra—

, —

Ar′

—

C(O)—

Ar′

—

, -Het′

-, —

Ar′

—

S—

Ar′

—

, —

Ar′

—

S(O)—

Ar′

—

, —

Ar′

—

S(O₂)—

Ar′

—

, and —

Ar′

-Q-Ar′

—

;

Ra is alkylene, Ar′

is arylene, each Ra′

is independently a group selected from the group consisting of alkylene, arylene, and a mixed alkylene/arylene group, Het′

is heteroarylene, and Q is a divalent group containing a quaternary carbon]), and

a substituted or unsubstituted branched monomer unit,

the monomer units each being bonded via a linking group represented by Formula (14),

-(G)b- 

 

(14)

(in the formula, G is a divalent group selected from the group consisting of —

O—

, —

R—

O—

R—

, —

S—

, —

NR—

, —

CR₂—

, —

SiR₂—

, —

SiR₂—

O—

SiR₂—

, and —

SiR₂—

O—

SiR₂—

O—

SiR₂—

(here, R is a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b is an integer of 0 or

     1).

4. The metal coordination compound-containing copolymer according to claim 1, wherein the copolymer comprises

a metal coordination compound monomer unit represented by any one of the Formulae (1) to (12), and

a substituted or unsubstituted conjugated monomer unit represented by Formula (13-2),

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;

a plurality of V, and R₁ and R₂, are independently substituents selected from the group consisting of —

R¹, —

OR², —

SR³, —

OCOR⁴, —

COOR⁵, and —

SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), may be identical to or different from each other, and are bonded to a substitutable position of an arylene or heteroarylene residue, and a and b are independently an integer of 0 or greater;

R₁ and R₂ may independently be a hydrogen atom;

n, m, and l are independently 0 or 1, and n, m, and l are not simultaneously

     0),

the monomer units each being bonded via a linking group represented by Formula (14),

-(G)b- 

 

(14)

(in the formula, G is a divalent group selected from the group consisting of —

O—

, —

R—

O—

R—

, —

S—

, —

NR—

, —

CR₂—

, —

SiR₂—

, —

SiR₂—

O—

SiR₂—

, and —

SiR₂—

O—

SiR₂—

O—

SiR₂—

(here, R is a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b is an integer of 0 or

     1).

5. The metal coordination compound-containing copolymer according to claim 1, wherein the copolymer comprises

a metal coordination compound monomer unit represented by any one of the Formulae (1) to (12),

a substituted or unsubstituted conjugated monomer unit represented by Formula (13-2),

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;

a plurality of V, and R₁ and R₂, are independently substituents selected from the group consisting of —

R¹, —

OR², —

SR³, —

OCOR⁴, —

COOR⁵, and —

SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), may be identical to or different from each other, and are bonded to a substitutable position of an arylene or heteroarylene residue, and a and b are independently an integer of 0 or greater;

R₁ and R₂ may independently be a hydrogen atom;

n, m, and l are independently 0 or 1, and n, m, and l are not simultaneously

     0), and

a substituted or unsubstituted branched monomer unit,

the monomer units each being bonded via a linking group represented by Formula (14),

-(G)b- 

 

(14)

(in the formula, G is a divalent group selected from the group consisting of —

O—

, —

R—

O—

R—

, —

S—

, —

NR—

, —

CR₂—

, —

SiR₂—

, —

SiR₂—

O—

SiR₂—

, and —

SiR₂—

O—

SiR₂—

O—

SiR₂—

(here, R is a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b is an integer of 0 or

     1).

6. The metal coordination compound-containing copolymer according to claim 1, wherein the substituted or unsubstituted branched monomer unit is a branched monomer unit selected from the group consisting of Formulae (15):

(in the formulae, a plurality of Y are substituents selected from the group consisting of —

R¹, —

OR², —

SR³, —

OCOR⁴, —

COOR⁵, and —

SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl or heteroaryl group), may be identical to or different from each other, and are bonded to a substitutable position of a benzene ring having a branched skeleton, and p is an integer of 0 to

     4).

7. The metal coordination compound-containing copolymer according to claim 1, wherein in the Formulae (1) to (12) ring A is pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazoletriazine, or isoquinoline, which may have a substituent that is the same as the groups defined by X₁ to X₇.

8. The metal coordination compound-containing copolymer according to claim 1, wherein in the Formulae (1) to (12) at least one of X₁ to X₇ and the substituent of ring A defined as being the same as X₁ to X₇ is a fluorine atom or a trifluoromethyl group.

9. The metal coordination compound-containing copolymer according to claim 1, wherein in the Formulae (1) to (12) M is iridium.

10. A polymer composition comprising the metal coordination compound-containing copolymer according to claim 1 and a conjugated or non-conjugated polymer.

11. An organic electroluminescent device fabricated using the metal coordination compound-containing copolymer according to claim 1.

12. An organic electroluminescent device fabricated using the polymer composition according to claim 10.