Platinum complexes

• US 20060094875A1
• Filed: 10/17/2003
• Published: 05/04/2006
• Est. Priority Date: 11/01/2002
• Status: Abandoned Application

• Current Assignee: Takasago International Corporation
• Original Assignee: Takasago International Corporation
• Inventors: Hori, Yoji, Itoh, Hisanori, Nakayama, Yuji, Matsushima, Yoshimasa
• Application Number:
  US10/533,303
• Publication Number:
  US 20060094875A1
• Time in Patent Office: Days
• US Class Current: 546/2
• CPC Class Codes: C07D 213/53 Nitrogen atoms
• CPC Class Codes: C07F 15/0093 without a metal-carbon linkage
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1011 Condensed systems
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/1033 with oxygen
• CPC Class Codes: C09K 2211/1037 with sulfur
• CPC Class Codes: C09K 2211/1044 containing two nitrogen atoms as heteroatoms
• CPC Class Codes: C09K 2211/1088 containing oxygen as the only heteroatom
• CPC Class Codes: C09K 2211/1092 containing sulfur 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: H10K 2101/10 Triplet emission
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 50/14 Carrier transporting layers
• CPC Class Codes: H10K 50/18 Carrier blocking layers
• CPC Class Codes: H10K 85/346 comprising platinum

Abstract

The invention aims at providing platinum complexes useful as materials for light emitting devices and extremely excellent in heat stability, luminous characteristics, and luminous efficiency, and a process for effective preparation thereof. The invention relates to platinum complexes represented by the general formula [1]: wherein any two of A, B and C are each independently an optionally substituted nitrogenous aromatic heterocyclic group and the other is optionally substituted aryl or optionally substituted heteroaryl; and Y is halogeno or an optionally substituted aryl or heteroaryl group which is bonded either directly or through oxygen (—O—) or sulfur (—S—) (with the proviso that when the adjacent two rings are nitrogenous aromatic heterocyclic groups, the cases wherein Y is chloro are excepted, while when the nonadjacent two rings are nitrogenous aromatic heterocyclic groups, the cases wherein Y is not halogeno are excepted).

Claims

1. A platinum complex represented by the following general formula [1]:

[where in the formula, any two of a ring A, a ring B, and a ring C each independently represent a nitrogen-containing aromatic heterocyclic group coordinating to a platinum atom through a nitrogen atom, which may be substituted, and the other represents an aryl group which may be substituted, or a heteroaryl group which may be substituted, and Y represents a halogen atom, or an aryl group which may be substituted, or a heteroaryl group which may be substituted, bonded directly or through an oxygen atom (—

O—

) or a sulfur atom (—

S—

) (provided that when the adjacent two rings are nitrogen-containing aromatic heterocyclic groups, the cases where Y is a chlorine atom are excluded, and that when the nonadjacent two rings are nitrogen-containing aromatic heterocyclic groups, the cases where Y is a group other than a halogen atom are excluded)].

2. The platinum complex according to claim 1, represented by the following general formula [1′

];

(wherein the formula, a ring A₁ and a ring B₁ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, a ring C₁ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and X represents a halogen atom.)

3. The platinum complex according to claim 2, represented by the following general formula [1a′

];

(where in the formula, a ring C′

¹ represents an aryl group or a heteroaryl group;

R¹, R², and R³ each independently represent a hydrogen atom, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or di-alkylamino group, a mono- or di-arylamino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heteroarylthio group, a sulfonyl group, a sulfinyl group, an ureido group, a phosphoramide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a substituted silyl group, or a polymerizable group;

further, a plurality of R¹s, a plurality of R²s, or/and a plurality of R³s may together form a fused ring with pyridine rings or the ring C to which they are bonded;

X represents a halogen atom;

m¹, m², and m³ represent numbers of the substituents R¹, R², and R³, respectively, and ml represents an integer of 0 to 3, and m² and m³ each represent an integer of 0 to 4; and

further, when m¹, m², and m³ each is an integer of 2 or more, a plurality of R¹s, a plurality of R²s, and a plurality of R³s may be mutually the same or different.)

4. The platinum complex according to claim 2 or 3, represented by the following general formula [1b′

];

(where in the formula, R¹, R², R³, X, m¹, m², and m³ represent the same meanings as described above.)

5. The platinum complex according to claim 1, represented by the following general formula [1″

];

(where in the formula, a ring B₂ and a ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, a ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted;

further, the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring; and

X¹ represents a fluorine atom, a bromine atom, or an iodine atom).

6. The platinum complex according to claim 5, represented by the following general formula [1a″

];

(where in the formula, a ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted;

R¹ and R³ each independently represent a hydrogen atom, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or di-alkylamino group, a mono- or di-arylamino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heteroarylthio group, a sulfonyl group, a sulfinyl group, an ureido group, a phosphoramide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a substituted silyl group, or a polymerizable group;

further, a plurality of R¹s or/and a plurality of R³s may together form a fused ring with pyridine rings to which they are bonded;

further, the ring B′

₂ and the ring C′

₂, and C′

₂ and the ring A₂, or the ring B′

₂, the ring C′

₂, and the ring A₂ may be mutually bonded to form a fused ring;

m¹ and m³ represent the numbers of the substituents R¹ and R³, respectively, and m¹ represents an integer of 0 to 3, and m³ represents an integer of 0 to 4; and

further, when m¹ and m³ are each an integer of 2 or more, a plurality of R¹s and a plurality of R³s may be mutually the same or different; and

X¹ is the same as described above).

7. The platinum complex according to claim 1, represented by the following general formula [1′

″

];

(where in the formula, a ring B₂ and a ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, a ring A₂ and a ring E each independently represent an aryl group which may be substituted, or a heteroaryl group which may be substituted;

the ring A₂ and the ring C₂, and the ring C₂ and the ring B₂, or the ring A₂, the ring C₂, and the ring B₂ may be mutually bonded to form a fused ring;

further, in the case where the ring A₂, the ring B₂, the ring C₂, or/and the ring E each have a substituent, when the substituent is a substituent capable of coordinating or bonding to a metal, a metal atom may be coordinated or bonded through a coordinatable or bondable atom in the substituent.)

8. The platinum complex according to claim 7, represented by the following general formula [1a′

″

];

(where in the formula, the ring A₂ and the ring E are the same as described above;

R¹ and R³ each independently represent an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or di-alkylamino group, a mono- or di-arylamino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heteroarylthio group, a sulfonyl group, a sulfinyl group, an ureido group, a phosphoramide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a substituted silyl group, or a polymerizable group;

further, R¹ and R³may together form a fused ring with two pyridine rings to which they are bonded;

R¹ and the ring A₂, or R¹, R³, and the ring A₂ may together form a fused ring;

m¹ and m³ represent the numbers of the substituents R¹ and R³, respectively, m¹ represents an integer of 0 to 3, and m³ represents an integer of 0 to 4; and

further, when m¹ and m³ are each an integer of 2 or more, a plurality of R¹s and a plurality of R³s may be mutually the same or different;

further, a plurality of R¹s or/and a plurality of R³s may together form a fused ring with the pyridine rings to which they are bonded; and

further when R¹, R³, and each substituent in the ring A₂ or/and the ring E are each a substituent capable of coordinating to a metal or capable of bonding to a metal, a metal atom may be coordinated or bonded through a coordinatable or bondable atom in the substituent.)

9. The platinum complex according to claim 7 or 8, represented by the following general formula [1b′

″

];

(where in the formula, R¹, R², R³, and R⁴ each independently represent an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or di-alkylamino group, a mono- or di-arylamino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heteroarylthio group, a sulfonyl group, a sulfinyl group, an ureido group, a phosphoramide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a substituted silyl group, or a polymerizable group;

further, R¹ and R², R¹ and R³, or/and R¹, R², and R³ may together form a fused ring with the two pyridine rings, or the pyridine ring and the benzene ring to which they are bonded;

m¹, m², m³, and m⁴ represent the numbers of the substituents R¹, R², R³, and R⁴, respectively, m¹ represents an integer of 0 to 3, m² and m³ each represent an integer of 0 to 4, and m⁴ represents an integer of 0 to 5; and

further, when m¹, m², m³, and m⁴ are each an integer of 2 or more, a plurality of R¹s, a plurality of R²s, a plurality of R³s, and a plurality of R⁴ may be mutually the same or different;

further, R¹s, R²s, R³s, or/and R⁴s may together form a fused ring with the pyridine rings or the benzene rings to which they are bonded; and

further when R¹, R², R³, and/or R⁴ are each a substituent capable of coordinating to a metal or capable of bonding to a metal, a metal atom may be coordinated or bonded through a coordinatable or bondable atom in the substituent.)

10. A method for producing the platinum complex according to claim 5, characterized by allowing a platinum diene complex represented by the general formula [2]:

Pt(X¹)₂(D) 

 

[2]

(where in the formula, D represents a nonconjugated diene compound, and X¹ represents a fluorine atom, a bromine atom, or an iodine atom) and a compound represented by the general formula [3];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring) to react with each other.

11. A method for producing the platinum complex according to claim 5, characterized by allowing a platinum diene complex represented by the general formula [2a]:

Pt(Cl)₂(D) 

 

[2a]

(where in the formula, D represents a nonconjugated diene compound), a compound represented by the general formula [3];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring), and a halogenating agent for substituting a halogen atom other than chlorine to mutually react.

12. The production method according to claim 11, wherein the platinum diene complex represented by the general formula [2a] is first allowed to react with the compound represented by the general formula [3], and then, allowed to react with the halogenating agent for substituting a halogen atom other than chlorine.

13. The production method according to claim 12, wherein the reaction of the platinum diene complex represented by the general formula [2a] and the compound represented by the general formula [3], and the subsequent reaction with the halogenating agent are carried out in one pot.

14. A method for producing the platinum complex according to claim 5, characterized by allowing a platinum complex represented by the general formula [1b″

];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring), and a halogenating agent for substituting a halogen atom other than chlorine to react with each other.

22. A method for producing the platinum complex according to claim 7, characterized by allowing a platinum diene complex represented by the general formula [2b]:

Pt(X)₂(D) 

 

[2b]

(where in the formula, D represents a nonconjugated diene compound, and X represents a halogen atom) and a compound represented by the general formula [3];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring) to react with each other, and thereby forming a platinum complex represented by the general formula [1c″

];

(where in the formula, the ring B₂, the ring C₂, the ring A₂, and X are the same as described above), and then, allowing a Grignard reagent represented by the general formula [4];

EMgX² 

 

[4]

(where in the formula, E represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and X² represents a halogen atom) to act thereon.

23. A method for producing the platinum complex according to claim 7, characterized by allowing a platinum compound represented by the general formula [5]:

M₂PtX₄ 

 

[5]

(where in the formula, M represents an alkali metal atom, and X represents a halogen atom.)) and a compound represented by the general formula [3];

(where in the formula, the ring B₂, the ring C₂, and the ring A₂ are the same as described above) to react with each other, and thereby forming a platinum complex represented by the general formula [1c″

];

(where in the formula, the ring B₂, the ring C₂, the ring A₂, and X are the same as described above), and then, allowing a Grignard reagent represented by the general formula [4];

EMgX² 

 

[4]

(where in the formula, E represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and X² represents a halogen atom) to act thereon.

24. A method for producing the platinum complex according to claim 7, characterized by, on a platinum diene complex represented by the general formula [2b]:

Pt(X)₂(D) 

 

[2b]

(where in the formula, D represents a nonconjugated diene compound, and X represents a halogen atom), allowing a Grignard reagent represented by the general formula [4];

EMgX² 

 

[4]

(where in the formula, E represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and X² represents a halogen atom) to act, and then, allowing a compound represented by the general formula [3];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring) to react therewith.

15. A method for producing a platinum complex having a tridentate ligand, and having a halogen atom, characterized by using a platinum diene complex represented by the general formula [2b]:

Pt(X)₂(D) 

 

[2b]

(where in the. formula, D represents a nonconjugated diene compound, and X represents a halogen atom) as a platinum source.

16. The production method according to claim 15, wherein the platinum complex having a tridentate ligand, and having a halogen atom is a platinum complex represented by the following general formula [1c″

];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring; and

X represents a halogen atom).

17. A method for producing a platinum complex represented by the general formula [1c″

];

(where in the formula, the ring B₂, the ring C₂, the ring A₂, and X are the same as described above.), characterized by allowing a platinum diene complex represented by the general formula [2b];

Pt(X)₂(D) 

 

[2b]

(where in the formula, D represents a nonconjugated diene compound, and X represents a halogen atom.) and a compound represented by the general formula [3];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring) to react with each other.

18. A method for producing a platinum complex represented by the general formula [1d″

];

(where in the formula, the ring B₂, the ring C₂, and the ring A₂ are the same as described above; and

X³ represents a halogen atom (provided that the cases where X and X³ are the same are excluded)), characterized by allowing a platinum diene complex represented by the general formula [2b];

Pt(X)₂(D) 

 

[2b]

(where in the formula, D represents a nonconjugated diene compound, and X represents a halogen atom), a compound represented by the general formula [3];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring), and a halogenating agent for substituting a halogen atom other than X to mutually react.

19. The production method according to claim 18, wherein the platinum diene complex represented by the general formula [2b] is first allowed to react with the compound represented by the general formula [3], and then, allowed to react with the halogenating agent for substituting a halogen atom other than X.

20. The production method according to claim 19, wherein the reaction of the platinum diene complex represented by the general formula [2b] and the compound represented by the general formula [3], and the subsequent reaction with the halogenating agent are carried out in one pot.

21. A method for producing a platinum complex represented by the general formula [1d″

];

(where in the formula, the ring B₂, the ring C₂, and the ring A₂ are the same as described above; and

X³ represents a halogen atom (provided that the cases where X and X³ are the same are excluded)), characterized by allowing a platinum complex represented by the general formula [1c″

];

(where in the formula, the ring B₂ and the ring C₂ each independently represent a nitrogen-containing aromatic heterocyclic group which may be substituted, the ring A₂ represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and the ring B₂ and the ring C₂, the ring C₂ and the ring A₂, or the ring B₂, the ring C₂, and the ring A₂ may be mutually bonded to form a fused ring; and

X represents a halogen atom), and a halogenating agent for substituting a halogen atom other than X to react with each other.