8-HYDROXYQUINOLINE-BASED WHITE-LIGHT-EMITTING ORGANIC ELECTROLUMINESCENT MATERIAL

• US 20110263856A1
• Filed: 09/07/2009
• Published: 10/27/2011
• Est. Priority Date: 01/12/2009
• Status: Active Grant

• Current Assignee: Taiyuan University Of Technology (Province of Shanxi)
• Original Assignee: Taiyuan University Of Technology (Province of Shanxi)
• Inventors: Wang, Hua, Hao, Yuying, Chen, Liuqing, Wei, Fangfang, Xu, Huixia, Xu, Bingshe, Fang, Xiaohong
• Granted Patent: US 8,455,643 B2
• Time in Patent Office: Days
• US Class Current: 546/6
• CPC Class Codes: C07D 401/06 linked by a carbon chain containing only aliphatic carbon atoms
• 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 2211/188 of other metals not provided for in one of the previous groups
• CPC Class Codes: H05B 33/10 Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
• CPC Class Codes: Y02B 20/00 Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

A white-light organic electroluminescent material based on 8-hydroxyquinoline and the method for preparing the same, as well as an organic light emitting diode including this material. The material may be the compound represented by the Formula (IX) having a DCDC group, a 5-position substituted 8-hydroxyquinolinyl group and a carbazolyl group as red light-, green light- and blue-light emitting groups, respectively. It exhibits a spectrum having a band width of 182.4 nm that substantially covers the visible-light region, and has a color coordinate of (0.3177, 0.3946), which just locates within the white-light area. Such a material is capable of realizing a white-light emission, and may be used in a white-light OLED as a single light-emitting layer, which can decrease the number of layers of the white-light OLED and thereby improve the luminous efficiency, stabilize the light color, lower the turn-on voltage and simplify the fabrication process.

Claims

1. A white-light organic electroluminescent material represented by the following Formula (I):

2. The white-light organic electroluminescent material according to claim 1, wherein M represents a divalent earth metal ion or a divalent transition metal ion.

3. The white-light organic electroluminescent material according to claim 1, wherein M represents Zn²⁺.

4. The white-light organic electroluminescent material according to claim 1, wherein A represents a 8-hydroxyquinolinyl group, B represents a carbazolyl group, and C represents a 3,3-dicyanomethylene-5,5-dimethyl-cyclohexenyl group.

5. The white-light organic electroluminescent material according to claim 1, wherein L₁ is a linking group which links the group A containing a 8-hydroxyquinolinyl group with the carbazolyl group B, and may be a saturated or unsaturated straight linking group having 2 to 8 carbon atoms;

and L₂ is a linking group which links the carbazolyl group B with the group C containing a 3,3-dicyanomethylene-1-cyclohexenyl group, and may be a saturated or unsaturated straight linking group having 2 to 8 carbon atoms.

6. The white-light organic electroluminescent material according to claim 1, wherein the carbazolyl group B is linked with the group A containing a 8-hydroxyquinolinyl group at its 4- or 5-position through the linking group L₁.

7. The white-light organic electroluminescent material according to claim 1, wherein each of the carbazolyl group B is linked with two groups C containing a 3,3-dicyanomethylene-1-cyclohexenyl group, and each of the two groups C containing a 3,3-dicyanomethylene-1-cyclohexenyl group is linked with the carbazolyl group B through the linking group L₂.

8. The white-light organic electroluminescent material according to claim 1, which has a structure represented by the following Formula (IX):

9. An organic light emitting diode comprising a light-emitting layer formed of the white-light organic electroluminescent material according to claim 1.

10. A method for preparing the white-light organic electroluminescent material according to claim 1, comprising the following steps:

(i) coupling a carbazolyl group B with a linking group L₁ to obtain a compound represented by the Formula (II);

B-L₁ 

 

(II)

(ii) coupling the compound represented by the Formula (II) with a group C containing a 3,3-dicyanomethylene-1-cyclohexenyl group through a linking group L₂ to obtain a compound represented by the Formula (III);

C-L₂-B-L₁ 

 

(III)

(iii) coupling the compound represented by the Formula (III) with a group A containing a 8-hydroxyquinolinyl group to obtain a compound represented by the Formula (IV);

C-L₂-B-L₁-A 

 

(IV)

(iv) chelating the compound represented by the Formula (IV) with a divalent metal ion M to obtain a compound represented by the in Formula (I);

11. The method according to claim 10, comprising the following steps:

(i-a) synthesizing N-(6-bromohexyl)-carbazole (BrRCz) from the starting material of carbazole and dibromohexane;

(i-b) preparing 3,6-diformyl-N-(6-bromohexyl)-carbazole (DFBrRCz) by reactiing BrRCz with POCl₃ and DMF;

(i-c) synthesizing 3,3-dicyanomethylene-5,5-dimethyl-cyclohexene (DCDC) by reacting isophorone with malononitrile; and

synthesizing 3,6-bis[2-(3,3-dicyanormethylene-5,5-dimethyl-cyclohexenyl)-ethenyl]-N-(6-bromohexyl)-carbazole (BrRCz-4CN) by reacting DCM with the DFBrRCz;

(ii-a) synthesizing 3,6-bis-[2-(3,3-dicyanomethylene-5,5-dimethyl-cyclohexenyl)-ethenyl]-N-[6-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)]-hexyl]-carbazole (BRCz-4CN) by reacting the BrRCz-4CN with 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxa-borane;

(ii-b) synthesizing 5-{3,6-bis[2-(3,3-dicyanomethylene-5,5-dimethyl-cyclohexenyl)-ethenyl]-N-(6-hexyl)-carbazolyl}-8-hydroxyquinoline (RCz-4CN-Q) by reacting the BRCz-4CN with 5-chloro-8-hydroxyquinoline;

(iii-c) synthesizing bi{5-{3,6-bis[2-(3,3-dicyanomethylene-5,5-dimethyl-cyclohexenyl)-ethenyl]-N-(6-hexyl)-carbazolyl}-8-hydroxyquinoline}zinc (Zn(RCz-4CN-Q)₂) by adding zinc acetate into the RCz-4CN-Q.

12. The method according to claim 10, comprising the following steps:

(i-a) adding 1,6-dibromohexane into a solution of carbazole in THF, adding a KOH solution dropwise during stirring in a molar ratio of carbazole 1,6-dibromohexane;

KOH=1;

1˜

3;

3˜

10 under a nitrogen atmosphere, and then reacting for 40˜

48 hours under reflux to synthesize the BrRCz;

(i-b) dissolving the BrRCz and DMF in 1,2-dichloroethane, adding POCl₃ into the resultant solution dropwise in an ice bath during stirring in a molar ratio of BrRCz;

DMF;

POCl₃=1;

2˜

3;

2˜

3, and after warming the resultant reaction mixture slowly, reacting for 20˜

24 hours under reflux to synthesize the DFBrRCz.

(i-c) adding isophorone and malononitrile into a mixed solution of glacial acetic acid, acetic anhydride, piperidine and DMF, stirring the resultant mixture at room temperature for 1˜

2 hours, warming up to 70˜

90°

C. and further stirring for 1˜

2 hours, and then adding DFBrRCz a molar ratio of DFBrRCz;

isophorone;

malononitrile=1;

2˜

8, and further reacting for 1˜

2 hours under 70˜

90°

to synthersize the BrRCz-4CN;

(ii-a) adding N-butyllithium dropwise into a BrRCz-4CN solution in THF in a cooling bath of mixed liquid nitrogen/butanol solution under a nitrogen atmosphere in a molar ratio of BrRCz-4CN;

2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxa-borane;

N-butyllithium=1;

1˜

2;

1˜

2, and then adding 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxa-borane quickly, stirring for 2˜

3 hours, warming up to the room temperature, and further reacting for 20˜

26 hours to synthesize the BRCz-4CN;

(ii-b) dissolving BRCz-4CN, Pd(PH₃)₄(O) and 5-chloro-8-hydroxyquinoline in ethylene glycol dimethyl ether in a molar ratio of BRCz-4CN;

5-chloro-8-hydroxyquinoline=1;

0.5˜

2 in the presence of the catalyst of Pd(PPH₃)₄(O) in an amount of 1/3˜

1/6 based on the amount of BRCz-4CN, adding equal volume based on the volume of ethylene glycol dimethyl ether of Na₂CO₃ aqueous solution in a concentration of 2 mol/L, and reacting for 20˜

26 hours under reflux to synthesize the RCz-4CN-Q;

(iii-c) dissolving RCz-4CN-Q and zinc acetate in anhydrous methanol in a molar ratio of 1˜

3;

1, and reacting for 3˜

5 hours under reflux to synthesize the Zn(RCz-4CN-Q)₂.

13. The method according to claim 10, wherein in the step (i-a), the amount of THF as solvent makes up 25˜

35% of the total reaction system, in the step (i-b) the amount of 1,2-dichloroethane as solvent makes up 80˜

90% of the total reaction system, in the step (ii-a) the amount of THF as solvent makes up 90˜

95% of the total reaction system, and in the step (ii-b) the amount of ethylene glycol dimethyl ether as solvent makes up 40˜

60% of the total reaction system.

14. The method according to claim 11, comprising the following steps:

(i-a) adding 1,6-dibromohexane into a solution of carbazole in THF, adding a KOH solution dropwise during stirring in a molar ratio of carbazole;

1,6-dibromohexane;

KOH=1;

1˜

3;

3˜

10 under a nitrogen atmosphere, and then reacting for 40˜

48 hours under reflux to synthesize the BrRCz;

(i-b) dissolving the BrRCz and DMF in 1,2-dichloroethane, adding POCl₃ into the resultant solution dropwise in an ice bath during stirring in a molar ratio of BrRCz;

DMF;

POCl₃=1;

2˜

3;

2˜

3, and after warming the resultant reaction mixture slowly, reacting for 20˜

24 hours under reflux to synthesize the DFBrRCz.

(i-c) adding isophorone and malononitrile into a mixed solution of glacial acetic acid, acetic anhydride, piperidine and DMF, stirring the resultant mixture at room temperature for 1˜

2 hours, warming up to 70˜

90°

C. and further stirring for 1˜

2 hours, and then adding DFBrRCz a molar ratio of DFBrRCz;

isophorone;

malononitrile=1;

2˜

8;

2˜

8, and further reacting for 1˜

2 hours under 70˜

90°

to synthersize the BrRCz-4CN;

(ii-a) adding N-butyllithium dropwise into a BrRCz-4CN solution in THF in a cooling bath of mixed liquid nitrogen/butanol solution under a nitrogen atmosphere in a molar ratio of BrRCz-4CN;

2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxa-borane;

N-butyllithium=1;

1˜

2;

1˜

2, and then adding 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxa-borane quickly, stirring for 2˜

3 hours, warming up to the room temperature, and further reacting for 20˜

26 hours to synthesize the BRCz-4CN;

(ii-b) dissolving BRCz-4CN, Pd(PH₃)₄(O) and 5-chloro-8-hydroxyquinoline in ethylene glycol dimethyl ether in a molar ratio of BRCz-4CN;

5-chloro-8-hydroxyquinoline=1;

0.5˜

2 in the presence of the catalyst of Pd(PPH₃)₄(O) in an amount of 1/3˜

1/6 based on the amount of BRCz-4CN, adding equal volume based on the volume of ethylene glycol dimethyl ether of Na₂CO₃ aqueous solution in a concentration of 2 mol/L, and reacting for 20˜

26 hours under reflux to synthesize the RCz-4CN-Q;

(iii-c) dissolving RCz-4CN-Q and zinc acetate in anhydrous methanol in a molar ratio of 1˜

3;

1, and reacting for 3˜

5 hours under reflux to synthesize the Zn(RCz-4CN-Q)₂.

15. The white-light organic electroluminescent material according to claim 2, wherein A represents a 8-hydroxyquinolinyl group, B represents a carbazolyl group, and C represents a 3,3-dicyanomethylene-5,5-dimethyl-cyclohexenyl group.

16. The white-light organic electroluminescent material according to claim 3, wherein A represents a 8-hydroxyquinolinyl group, B represents a carbazolyl group, and C represents a 3,3-dicyanomethylene-5,5-dimethyl-cyclohexenyl group.