Lin Xiongjie, Tang Danting, He Tian, Xu Zheng, Qiu Huayu, Zhang Qian, Yin Shouchun
College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, PR China.
College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2019 Jun 15;217:164-169. doi: 10.1016/j.saa.2019.03.084. Epub 2019 Mar 26.
A series of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) with different connection sites and conjugation length and fluorene alternating conjugated polymers have been synthesized via palladium-catalyzed Suzuki coupling reaction. The polymers were fully characterized by H NMR spectroscopy and gel permeation chromatography (GPC), and their properties were measured by thermogravimetric analysis (TGA), UV-vis absorption spectroscopy, cyclic voltammetry (CV), photoluminescence (PL) spectroscopy, the Z-scan technique, and theoretical calculation using density-functional theory (DFT) method. The results indicate that the connection sites and conjugation length of BODIPY have great effect on the optical-electronic and nonlinear optical properties of the conjugated BODIPY- fluorene copolymers although they don't affect the polymerization process. The absorption and emission peaks of P1 exhibit red shifts compared to those of P2 and P3. The polymers show good nonlinear optical properties that are closely related to the connection sites of the BODIPY pendants. P1 exhibits relatively richer nonlinear optical (NLO) properties than P2 and P3. The third order nonlinear optical coefficient (χ) of P1 is 3.57 × 10 esu, which is ~4 times larger than those of P2 and P3.
通过钯催化的铃木偶联反应合成了一系列具有不同连接位点、共轭长度的4,4-二氟-4-硼-3a,4a-二氮杂-s-茚（BODIPY）与芴交替共轭聚合物。通过核磁共振氢谱（H NMR）和凝胶渗透色谱法（GPC）对聚合物进行了全面表征，并通过热重分析（TGA）、紫外-可见吸收光谱、循环伏安法（CV）、光致发光（PL）光谱、Z扫描技术以及使用密度泛函理论（DFT）方法的理论计算对其性能进行了测定。结果表明，BODIPY的连接位点和共轭长度对共轭BODIPY-芴共聚物的光电和非线性光学性质有很大影响，尽管它们不影响聚合过程。与P2和P3相比，P1的吸收峰和发射峰出现红移。这些聚合物表现出良好的非线性光学性质，这与BODIPY侧基的连接位点密切相关。P1表现出比P2和P3相对更丰富的非线性光学（NLO）性质。P1的三阶非线性光学系数（χ）为3.57×10 esu，约为P2和P3的4倍。
