涂覆有低聚噻吩的星形开环易位聚合聚合物，其具有独特的发射特性。
Star-Shaped ROMP Polymers Coated with Oligothiophenes That Exhibit Unique Emission.
作者信息
Sun Zelin, Kobori Ken, Nomura Kotohiro, Asano Motoko S
机构信息
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Minami Osawa, Hachioji, Tokyo 192-0397, Japan.
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Tenjincho, Kiryu, Gunma 376-8515, Japan.
出版信息
ACS Omega. 2022 Apr 5;7(15):13270-13279. doi: 10.1021/acsomega.2c00739. eCollection 2022 Apr 19.
A series of oligo(thiophene)-modified "soluble" star-shaped ring-opening metathesis polymerization (ROMP) polymers were prepared by sequential living ROMP of norbornene and a cross-linking agent using a molybdenum-alkylidene catalyst, followed by Wittig-type coupling for termination with oligo(thiophene) carboxaldehydes. The resultant star-shaped ROMP polymers displayed unique emission properties affected by the core size and arm repeat units as well as the kind of oligothiophene coated. The effects of the thiophene groups on photophysical properties of star-shaped/linear polymers were studied time-resolved fluorescence spectroscopy. Fluorescence lifetimes were determined in THF as 400, 640, 730, and 820 ps for , , and , respectively. A significant enhancement of the nonradiative rate constants in the star-shaped polymers results in relatively lower fluorescence quantum yields and shorter fluorescence lifetimes compared to the corresponding linear polymers.
通过使用钼亚烷基催化剂对降冰片烯和交联剂进行连续活性开环易位聚合（ROMP），然后用寡聚（噻吩）甲醛进行维蒂希型偶联终止反应，制备了一系列寡聚（噻吩）修饰的“可溶性”星形开环易位聚合（ROMP）聚合物。所得的星形ROMP聚合物表现出独特的发射特性，这些特性受核心尺寸、臂重复单元以及所包覆的寡聚噻吩种类的影响。通过时间分辨荧光光谱研究了噻吩基团对星形/线性聚合物光物理性质的影响。在四氢呋喃中测定的荧光寿命分别为：对于[具体聚合物1]为400皮秒、对于[具体聚合物2]为640皮秒、对于[具体聚合物3]为730皮秒、对于[具体聚合物4]为820皮秒。与相应的线性聚合物相比，星形聚合物中非辐射速率常数[具体符号]的显著提高导致荧光量子产率相对较低且荧光寿命较短。
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