Metal-free, regioselective diyne polycyclotrimerization: Synthesis, photoluminescence, solvatochromism, and two-photon absorption of a triphenylamine-containing hyperbranched poly(aroylarylene)
Metal-free, regioselective diyne polycyclotrimerization: Synthesis, photoluminescence, solvatochromism, and two-photon absorption of a triphenylamine-containing hyperbranched poly(aroylarylene)
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无金属、区域选择性二炔多环三聚：含三苯胺的超支化聚（芳酰亚芳基）的合成、光致发光、溶剂化变色和双光子吸收
DOI：
10.1021/ma070200w
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发表时间：
2007-06
期刊：
影响因子：
5.5
通讯作者：
Tang, Ben Zhong
中科院分区：
文献类型：
--
作者：
Dong, Hongchen;Williams, Ian D.;Lu, Weixin;Haussler, Matthias;Sung, Herman H. Y.;Wong, George K. L.;Dong, Yongqiang;Lam, Jacky W. Y.;Qin, Anjun;Jim, Cathy K. W.;Tang, Ben Zhong
以N，N-二（4-乙炔基羰基苯基）苯胺（1）为原料，通过无金属环三聚反应，合成了一种具有1，3，5-区域规整性的超支化聚芳酰亚芳基（hb-P1）。该聚合物可溶于常见的有机溶剂，如THF和氯仿，并且是热稳定的，当加热到高达450 °C的温度时，其重量损失5%。该聚合物是荧光和溶剂化变色的，其发射颜色从甲苯中的455 nm（蓝色）变为DMF中的549 nm（黄色）。该聚合物表现出大的双光子吸收截面，由于其给电子TPA和吸电子的1，3，5-三羰基苯基团之间的分子内电荷转移。
A hyperbranched poly(aroylarylene) containing triphenylamine (TPA) moiety (hb-P1) is synthesized by metal-free polycyclotrimerization of N,N-bis(4-ethynylcarbonylphenyl)aniline (1) in a high yield (86%) with a perfect 1,3,5-regioregularity. The polymer is soluble in common organic solvents such as THF and chloroform and is thermally stable, losing 5% of its weight when heated to a temperature as high as ∼450 °C. The polymer is fluorescent and solvatochromic, whose emission color changes from ∼455 nm (blue) in toluene to 549 nm (yellow) in DMF. The polymer exhibits a large two-photon absorption cross-section due to the intramolecular charge transfer between its electron-donating TPA and electron-withdrawing 1,3,5-tricarbonylbenzene groups.