Nomura Kotohiro, Miwata Tomohiro, Shinozuka Takuya, Morita Munetsugu, Geerts Yves H, Fujiki Michiya, Asano Motoko S
Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan.
Division of Molecular Science, School of Science and Engineering, Gunma University, 1-5-1, Ten-jincho, Kiryu, Gunma 376-8515, Japan.
ACS Omega. 2018 May 9;3(5):5052-5063. doi: 10.1021/acsomega.8b00676. eCollection 2018 May 31.
Optical properties of three types of terthiophene (3T) functionalized conjugated triarm (star-shaped) polymers consisting of poly(9,9-di--octyl-fluorene-2,7-vinylene) (PFV) arms and different [2,4,6-tri(biphenyl)benzene (TBP), 1,3,5-tri(benzyl)benzene (TBB), and triphenylamine (TPA)] cores, prepared by combined olefin metathesis with Wittig coupling, have been studied. Relative intensities [increases in the higher vibronic bands, (0, 1) fluorescence (FL)] of the fully conjugated TPA-core polymers, TPA(PFV-3T), in the fluorescence (FL) spectra in tetrahydrofuran (toluene) solution were higher than those in the other triarm polymers, TBP(PFV-3T), TBB(PFV-3T), whereas no significant differences were observed in their UV-vis spectra; notable temperature dependences were not observed in the UV-vis and FL spectra (at -5, 25, and 55 °C). Remarkable differences were not observed in the spectra in these polymer thin films, whereas λ values red-shifted due to the formation of -type aggregates. The observation for the time-resolved study well corresponds to results for the steady-state fluorescence measurements. The observed unique emission by the star-shaped (triarm) polymer containing the TPA core would be assumed to be due to a difference in nature of the core (higher coplanarity) compared to that of the others.
通过烯烃复分解与维蒂希偶联相结合制备了三种由聚(9,9 - 二 - 辛基 - 芴 - 2,7 - 亚乙烯基)(PFV)臂和不同[2,4,6 - 三(联苯)苯(TBP)、1,3,5 - 三(苄基)苯(TBB)和三苯胺(TPA)]核组成的噻吩并[3,2 - b]噻吩(3T)功能化共轭三臂(星形)聚合物,并对其光学性质进行了研究。在四氢呋喃(甲苯)溶液中的荧光(FL)光谱中,完全共轭的TPA核聚合物TPA(PFV - 3T)的相对强度[较高振动带(0,1)荧光(FL)增加]高于其他三臂聚合物TBP(PFV - 3T)、TBB(PFV - 3T),而它们的紫外 - 可见光谱未观察到显著差异;在紫外 - 可见和FL光谱中(在 - 5、25和55°C)未观察到明显的温度依赖性。在这些聚合物薄膜的光谱中未观察到显著差异,而由于 - 型聚集体的形成,λ值发生红移。时间分辨研究的观察结果与稳态荧光测量结果非常吻合。含有TPA核的星形(三臂)聚合物观察到的独特发射被认为是由于其核的性质(更高的共平面性)与其他核不同所致。