Poly(thienothiophenylborane)s and poly(dithienothiophenylborane)s for white light emitting diodes

Abstract

The present invention discloses the syntheses of new polymers with defined structures, comprising dithienothiophene (DTT) and thienothiophene (TT) derivatives and boron, light emitting devices of which have wide spectrum of fluorescence at visible region and potential of emitting white light.

Claims

1. A polymer comprising one or more formulas selected from the group consisting of formulas (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) ##STR00010## ##STR00011## where, ##STR00012## n=1-1,000,000 inclusive; and R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are atom chain(s) of about 1 atom to 60 atoms; wherein, R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 may contain one or more functional group selected from the group consisting of alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

2. A polymer comprising one or more formulas selected from the group consisting of formulas (XI), (XII), (XIII), (XIV) and (XV) ##STR00013## where, ##STR00014## n=1-1,000,000 inclusive; and R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are atom chain(s) of about 1 atom to 60 atoms; wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 may contain one or more functional group selected from the group consisting of alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

3. A polymer comprising one or more formulas selected from the group consisting of formulas (XVI), (XVII), (XVIII), (XIX), (XXII), (XXIII), (XXIV), (XXV), (XXVI) and (XXVII) ##STR00015## ##STR00016## where, ##STR00017## n=1-1,000,000 inclusive; and R, R.sup.1, R.sup.2, and R.sup.3 are atom chain(s)/group(s) of about 1 atom to 60 atoms; wherein, R, R.sup.1, R.sup.2, and R.sup.3 may contain one or more functional group selected from the group consisting of alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

4. A polymer comprising one or more formulas selected from the group consisting of formulas (XXVIII), (XXIX), (XXX), (XXXI), (XXXII), (XXXIII), (XXXIV), (XXXV), and (XXXVII) ##STR00018## ##STR00019## where, ##STR00020## n=1-1,000,000 inclusive; and R, R.sup.1, R.sup.2, and R.sup.3 are atom chain(s)/group(s) of about 1 atom to 60 atoms; wherein, R, R.sup.1, R.sup.2, and R.sup.3 may contain one or more functional group selected from the group consisting of alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

5. A blend comprising a polymer given in any one of claims 1 to 4.

6. A formulation comprising a polymer given in any one of claims 1 to 4.

7. A polymer comprising formula I ##STR00021## where, ##STR00022## n=2-1,000,000 inclusive; and R, and R.sup.1 are atom chain(s) of about 1 atom to 60 atoms; wherein, R and R.sup.1 contain one or more functional group selected from the group consisting of aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

Description

DISCLOSURE OF THE INVENTION

(1) The invention discloses the compounds that are useful when employed as organic light emitting materials, i. e. organic light emitting diodes (OLED), to emit particularly white light. They have potential of being employed as charge transport materials in electronic devices such as organic field effect transistors (OFET), organic photovoltaic diodes and the like. The invention discloses the compounds having the formulas (I)-(X), (XI)-(XV), (XVI)-(XXVII) and (XXVIII)-(XXXVII).

(2) ##STR00001## ##STR00002##
wherein
R, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently or equally atom chain(s)/group(s) of about 1 atom to 60 atoms. They may equally or independently have one or more of a group comprising alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

(3) ##STR00003##
wherein
R, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently or equally atom chain(s)/group(s) of about 1 atom to 60 atoms. They may equally or independently have one or more of a group comprising alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

(4) ##STR00004## ##STR00005##
wherein
R, R.sup.1, R.sup.2 and R.sup.3 are independently or equally atom chain(s)/group(s) of about 1 atom to 60 atoms. They may equally or independently have one or more of a group comprising alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

(5) ##STR00006## ##STR00007##
wherein
R, R.sup.1, R.sup.2 and R.sup.3 are independently or equally atom chain(s)/group(s) of about 1 atom to 60 atoms. They may equally or independently have one or more of a group comprising alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

(6) ##STR00008## ##STR00009##
wherein
R, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently or equally atom chain(s)/group(s) of about 1 atom to 60 atoms. They may equally or independently have one or more of a group comprising alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

(7) Dithienothiophenes (DTT) (XXXVIII)-(XLIII) and thienothiophenes (TT) (XLIV)-(XLVII) were synthesized following the literature procedure (T. Ozturk, et al. Tetrahedron, 2005, 61, 11055; E. Ertas, et al. Tetrahedron Lett. 2004, 45, 3405; I. Osken, Tetrahedron, 2012, 68, 1216; P. Dundar, Synth. Met. 2012, 162, 1010; I. Osken, Thin Solid Films, 2011, 519, 7707; O. Sahin, Synth. Met. 2011, 161, 183; O. Mert, J. Electroanal. Chem. 2006, 591, 53; A. Capan, Macromolecules 2012, 45, 8228). Corresponding polymers (I)-(X) of DTTs and TTs were produced by lithiating bromo-DTTs (XXXVI)-(XLI) and TTs (XLII)-(XLV) with n-BuLi, which was followed by addition of aryldimethoxyborane. The DTT analogues comprising Se heteroatom(s), the DTTs having sulfurs in the rings looking at the same direction, TT analogues comprising Se atom(s) and TTs having sulfurs in the rings looking at the same direction were synthesized following the literature method (Gronowitz, S.; Persson, B. Acta Chem. Scand. 1967, 21, 812-813; WO2008/077465).

EXAMPLE

(8) A General Procedure for the Synthesis of the Polymers; Polymer (VIII, Ar=Mesityl, R.sup.4=H).

(9) To a solution of thienothiophene (TT) (XLV, R.sup.4=H) (0.2 g, 0.44 mmol) dissolved in dry THF (30 ml) under N.sub.2, n-BuLi (0.8 ml, 3.3 mmol, 1.9 M) was added dropwise at ?78? C., and the mixture was stirred one and half hour. The addition could be performed at any temperature between ?78-+30? C. Then, the temperature was raised to room temperature and the mixture was stirred at this temperature for 20 min. Dimethoxymesityl borane (MesB(OMe).sub.2) (0.170 g, 0.88 mmol), dissolved in dry THF (5 ml) was added under nitrogen atmosphere. The reaction was stirred overnight and the solvent was removed under reduced pressure. The stirring could be between 1 minovernight or longer, and dimethoxymesityl borane could be dissolved in any organic solvent, which does not react with dimethoxymesityl borane. The residue was dissolved in minimum amount of THF and precipitated in methanol. The precipitate was filtered and washed with methanol. Mw: 146600, Mn: 102800, Mw/Mn: 1.43, dn/dc: 0.16 mL/g (THF, 25? C.).

(10) Example of a Device Fabrication:

(11) Organic light emitting devices were fabricated by coating the polymers from their solution onto electrically conductive substrates. The polymer (VIII) was dissolved in a mixture of toluene/dichlorobenzene (8 mg/ml). Indium thin oxide (ITO), coated (15 ohms/sq.) on a glass, was employed as an anode electrode. PEDOT:PSS, as a hole injection layer, was spin-coated on ITO, which was dried at 110? C. for 10 min. Subsequently, polymer film, as an active layer, was coated by spin coating. Finally, LiF (1 nm) and aluminum (Al, 100 nm) was deposited under vacuum (?10.sup.?6 mbar) by thermal evaporation technique to assemble the cathode electrodes.

DESCRIPTION OF DRAWINGS

(12) FIG. 1. UV spectrum of polymer (VIII) in THF

(13) FIG. 2. Fluorescence spectrum of polymer (VIII) in THF

(14) FIG. 3. a) Electroluminescent spectrum of the fabricated device of the polymer VIII (device layout: PEDOT/VIII/LiF/Al), b) CIE coordinates of the fabricated device of the polymer VIII at different voltages. The electroluminescent spectrum covers the region almost from 350 nm to 950 nm. Color coordinates are in the region for white color according to the CIE 1931 Chromaticity Diagram.

(15) FIG. 4. OLED device characteristics: a) voltage-current b) luminance-voltage c) luminous efficiency-current density and d) external quantum efficiency-current density.