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

1)新型含氮聚乙炔的合成及性能合成了N-咔唑乙炔(CA)和3-吲哚基-1-丙炔(IP)等新型含氮乙炔。 CA 通过 WCID26D2 或 WCID26D2-n-BuD24D2Sn 聚合，以良好的收率得到聚合物 (D21-4x10D1)。另一方面，通过使用[(nbd)RhCl]D2进行IP聚合以高产率提供D2为1.3×10D1的聚合物。在紫外-可见光谱中，与聚苯乙炔相比，聚(CA)显示出较大的红移（截止~700nm）。这一结果归因于聚合物主链的广泛共轭。 Poly(CA)的三阶磁化系数为18×10，在取代聚乙炔中是一个非常大的值。2)具有二烷基氨基的聚苯乙炔的合成及性能将两个具有对-n-N,N-二乙氨基和对-n-N,N-二丁氨基的苯乙炔在[(nbd)RhCl]300-400 nm下聚合。聚合物薄膜的电化学掺杂导致吸收偏移到680 nm左右的区域，同时聚合物薄膜的颜色从赭石色变为深蓝色。 3）取代聚乙炔的光致发光和电致发光研究了各种取代聚乙炔的电致发光（EL）和光致发光（PL）。分别用聚(二苯乙炔)衍生物和聚(1-烷基-2-苯乙炔)衍生物观察到强绿色和蓝色EL。另一方面，单取代乙炔聚合物表现出非常弱的 PL 和 EL。阐明了PL和EL的波长和强度对取代基结构分子的依赖性。在强烈激发下，还观察到由于受激发射而引起的显着光谱变窄。

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.