Design, synthesis, and properties of nonlinear optical chromophores based on a verbenone bridge with a novel dendritic acceptor
Design, synthesis, and properties of nonlinear optical chromophores based on a verbenone bridge with a novel dendritic acceptor
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DOI：
10.1039/c8tc00083b
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发表时间：
2018-03
影响因子：
6.4
通讯作者：
Hejing Sun;Zhong’an Li;Jieyun Wu;Zhenhua Jiang;Jingdong Luo;A. Jen
中科院分区：
文献类型：
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作者：
Hejing Sun;Zhong’an Li;Jieyun Wu;Zhenhua Jiang;Jingdong Luo;A. Jen
以N，N-二乙基苯胺为给体，马鞭草烯酮为桥环，三氰基呋喃（TCF）或三氰基呋喃衍生物为受体，合成了两种新型的二阶非线性光学（NLO）生色团，并对其结构进行了系统表征.此外，还发展了一种简便实用的非线性光学树枝状受体的合成方法。与C7相比，在受体分子中引入树枝状衍生物空间位阻基团后，发色团C8具有较好的热稳定性，其热分解温度比发色团C7高33 °C。同时，循环伏安法（CV）实验进行，以确定不同的氧化还原性能。紫外-可见-近红外吸收光谱表明，两种发色团中的共轭马鞭草烯酮四烯链段均能显著提高发色团的玻璃形成能力和分子偏振性。与传统的隔离基团相比，通过短C-C键连接的庞大的树枝状部分更接近TCF受体，TCF受体是发色团中最极性的部分。从电光系数得到的结果表明，这种TCF受体具有独特的树枝状结构，可以防止发色团之间的反平行包装，提高极化效率，提高电光性能。这些性质，以及良好的溶解性，表明这些新的发色团作为先进的光子器件的材料的潜在用途。
Two novel second order nonlinear optical (NLO) chromophores based on N,N-diethylaniline as a donor, verbenone based tetraene as a bridge, and tricyanofuran (TCF) or tricyanofuran derivatives with a dendritic moiety as an acceptor have been synthesized in good overall yields and systematically characterized. Besides, a facile applicable synthetic approach for a NLO dendritic acceptor was developed. Compared with C7, after introducing dendritic derivative steric hindrance groups into the acceptor, chromophore C8 had good thermal stabilities with high thermal decomposition temperatures which were 33 °C higher than that of chromophore C7. At the same time, cyclic voltammetry (CV) experiments were performed to determine the different redox properties. The conjugated verbenone tetraene segments in two chromophores could significantly improve the glass-forming ability and molecular polarization of chromophores as revealed by UV-vis-NIR absorption measurements. The bulky dendritic moiety linked by a short C–C bond is closer to the TCF acceptor, which is the most polar part in the chromophore, compared to conventional isolation groups. The results obtained from electro-optic (EO) coefficients indicate that this TCF acceptor with a unique dendritic structure can prevent antiparallel packing between chromophores, improving the poling efficiency and enhancing the EO performance. These properties, together with the good solubility, suggest the potential use of these new chromophores as materials for advanced photonic devices.