Electroluminescent Metal Complexes With Triazoles And Benzotriazoles

• US 20080015355A1
• Filed: 06/20/2005
• Published: 01/17/2008
• Est. Priority Date: 06/28/2004
• Status: Active Grant

• Current Assignee: UDC Ireland Limited (Universal Display Corporation)
• Original Assignee: BASF SE
• Inventors: Schafer, Thomas, Schmidhalter, Beat, Pretot, Roger, Bardon, Kristina
• Granted Patent: US 7,820,828 B2
• Time in Patent Office: Days
• US Class Current: 546/4
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/185 of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• 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 85/346 comprising platinum

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

1. A compound of the formula

2. The compound of claim 1, wherein the metal M¹ is selected from the group consisting of Fe, Ru, Ni, Co, Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Ag and Au.

3. The compound of claim 1 having the formula:

M²L^a(L^b)_w(L^c)_x(L′

)_y(L″

)_z, 

 

(II), wherein

w=0 or 1, x=0 or 1, y=0, 1 or 2, and z=0 or 1,

M² is Pt. Pd, Rh, Re, or Ir,

L′

is a bidentate ligand or a monodentate ligand;

with the proviso that;

when L′

is a monodentate ligand, y+z=2, and when L′

is a bidentate ligand, z=0;

L″

is a monodentate ligand; and

L^a, L^b and L^c are alike or different from each other and each of L^a, L^b and L^c has the structure (IIIa), (IIIb), or (IV) below;

Q¹ and Q² are independently of each other hydrogen, C₁-C₂₄alkyl, or C₆-C₁₈aryl, which is optionally substituted by G;

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

A²² and A²³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁵, A⁴⁶ and A⁴⁷ 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, A¹², A¹³, A¹⁴, A¹⁵ and A¹⁶ are independently of each other H, CN, halogen, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, C₆-C₁₈aryl, —

NR²⁵R²⁶, —

CONR²⁵R²⁶, or —

COOR²⁷, or C₂-C₁₀heteroaryl, which is optionally substituted by G;

wherein

E¹ is O, S, or NR²⁵,

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

Y¹, Y² and Y³ are independently of each other a group of formula

wherein

R⁴¹ is the bond to M²,

R⁷¹ is the bond to M²,

R⁴² is hydrogen, or C₁-C₂₄alkyl, CN, C₁-C₂₄alkyl, which is substituted by F or halogen,

C₆-C₁₈-aryl, C₆-C₁₈-aryl which is substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy,

R⁴³ is hydrogen, CN, halogen, C₁-C₂₄alkyl, which is substituted by F, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy, —

CONR²⁵R²⁶, —

COOR²⁷,

wherein

E² is —

S—

, —

O—

, or —

NR^25′

—

, wherein R^25′

is C₁-C₂₄alkyl, or C₆-C₁₀aryl,

R¹¹⁰ is H, CN, C₁-C₂₄alkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, —

NR²⁵R²⁶, —

CONR²⁵R²⁶, or —

COOR²⁷ or

R⁴² and R⁴³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, A⁴⁶ and A⁴⁷ 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, which is substituted by F, halogen,

C₆-C₁₈-aryl, C₆-C₁₈-aryl which is substituted by C₁-C₁₂ alkyl, or C₁-C₈alkoxy,

R⁴⁵ is hydrogen, CN or C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted by F, halogen, C₆-C₁₈-aryl, C₆-C₁₈-aryl which is substituted by C₁-C₁₂ alkyl, or C₁-C₈alkoxy,

A^11′

, A^12′

, A^13′

, and A^14′

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, heptyl, 2-ethylhexyl, and octyl, which can 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, NR³⁰⁵R³⁰⁶CONR³⁰⁵R³⁰⁶, 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 or

4. The compound of claim 3, wherein w=1, x=1, y=0, and z=0 and M² is Rh, Re, or Ir.

5. The compound of claim 1, wherein the bidentate ligand L¹ or L′

is a compound of formula

6. The compound of claim 1 having a structure (Va), (Vb), (Vc), (Vd), (VIa), or (VIb) below:

7. The compound of claim 6 of the formulae:

8. An organic electronic device, comprising an emitting layer wherein the emitting layer comprises a compound according to claim 1.

9. The device of claim 8, 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.

10. (canceled)