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Synthesis of Novel Conjugated Polymers from Substituted Acetylenes and Development of their Optoelectronic Functions

取代乙炔新型共轭聚合物的合成及其光电功能的开发

基本信息

批准号：
09450350
负责人：
MASUDA Toshio
金额：
$ 7.81万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

1) Synthesis and Properties of Novel Nitrogen-Containing PolyacetylenesNovel nitrogen-containing acetylenes such as N-Carbazolylacetylene(CA)and 3-indolyl-1-propyne(IP)were synthesized. CA was polymerized by WCIィイD26ィエD2 or WCIィイD26ィエD2-n-BuィイD24ィエD2Sn to give polymer (MィイD2wィエD21-4x10ィイD14ィエD1) in good yield. On the other hand, polymerization of IP by using [(nbd)RhCl] ィイD22ィエD2 afforded polymer having MィイD2wィエD2 of 1.3x10ィイD15ィエD1 in high yield. In the UV-visible spectrum, poly (CA) exhibited a large red shift (cutoff〜700nm) compared with that of poly (phenylacetylene). This result was attributed to widely conjugated main chain of the polymer. Poly (CA) showed a third-order susceptibility of 18x10ィイD1-12ィエD1 esu, a very large value among substituted polyacetylenes.2) Synthesis and Properties of Poly (phenylacetylene) s Having Dialkylamino GroupsTwo phenylacetylenes having p-n-N, N-diethylamino and p-n-N, N-dibutylamino groups were polymerized by [(nbd) RhCl] ィイD22ィエD2-EtィイD23ィエD2N catalyst to give polymers in high yield. These polymers were soluble in CHClィイD23ィエD2. In the UV-visible spectra, they showed absorption maxima around 300-400 nm. Electrochemical doping of the polymer films resulted in the shift of the absorptions to a region around 680 nm, which was accompanied by a color change of the polymer films from green ocher to deep blue.3) Photoluminescence and Electroluminescence of Substituted PolyacetylenesElectroluminescnescence (EL) and photoluminescence (PL) of various substituted polyacetylenes were examined. Intense green and blue EL were observed with poly (diphenylacetylene) derivatives and poly (1-alkyl-2-phenylacetylene) derivatives, respectively. On the other hand, monosubstituted acetylene polymers showed very weak PL and EL. The dependence of wavelength and intensity of PL and EL on the molecular structure of substituents were clarified. Upon intense excitation, remarkable spectral narrowing due to stimulated emission was also observed.

1)新型含氮聚乙炔的合成与性能研究合成了N-咔唑乙炔(CA)和3-吲哚-1-丙炔(IP)等新型含氮乙炔。CA由WCIィイD26ィエD2或WCIィイD26ィエD2-n-BuィイD24ィエD2Sn聚合而成(MィイD2wィエD21-4x10ィイD14ィエD1)，产率较高。另一方面，用[(Nbd)RhCl2]ィイD22ィエD2进行IP聚合，得到了高产率的聚合物，其MィイD2wィエD2为1.3×10ィイD15ィエD1。在紫外-可见光谱中，聚(CA)与聚苯乙炔相比有较大的红移(截止到700 nm)。这一结果归因于聚合物主链的广泛共轭。聚(CA)的三阶极化率为18x10ィイD_1-12ィエD_1esu，在取代的聚乙炔中具有很大的三阶极化率。2)含二烷基氨基的聚苯乙炔的合成与性质[(Nbd)ィイ]ィイD22ィエD_2-etィイD_(23)ィエD_2N催化聚合了两种含p-n-N，N-二乙氨基和p-n-N，N-二丁氨基的苯乙炔。这些聚合物可溶于CHClィイD23ィエD2。在紫外可见光谱中，它们的最大吸收波长在300-400 nm之间。电化学掺杂导致聚合物膜的吸收向680 nm附近移动，并伴随着聚合物膜的颜色从绿色向深蓝色的变化。3)研究了取代聚乙炔的光致发光和电致发光。聚二苯乙炔衍生物和聚1-烷基-2-苯乙炔衍生物分别产生了强烈的绿色和蓝色电致发光。另一方面，单取代乙炔聚合物表现出很弱的发光和电致发光。阐明了荧光和电致发光的波长和强度与取代基的分子结构的关系。在强激发下，由于受激发射也观察到了显著的光谱窄化。