Department of Chemistry, Hubei Key Laboratory on Organic and Polymeric Opto-Electronic Materials, Wuhan University, Wuhan 430072, China.
Chemistry. 2013 May 17;19(21):6874-88. doi: 10.1002/chem.201203567. Epub 2013 Mar 27.
Through the combination of the divergent and convergent approaches, coupled with the utilization of the powerful Sharpless "click-chemistry" reaction, two series of sulfonyl-based high-generation NLO dendrimers were conveniently prepared with high purity and in satisfactory yields. Thanks to the perfect three-dimensional (3D) spatial isolation from the highly branched structure and the isolation effect of the exterior benzene moieties and the interior triazole rings, these dendrimers exhibited large second harmonic generation coefficient (d33) values up to 181 pm V(-1), which, to the best of our knowledge, is the highest value so far for polymers containing sulfonyl-based chromophore moieties. Meanwhile, compared with the nitro-chromophore-based analogues, their optical transparency and NLO stability were improved in a large degree, due to the lower dipole moment (μ) and the special main-chain structure of sulfonyl-based chromophore in these dendrimers.
通过发散和收敛方法的结合,再加上利用强大的 Sharpless“点击化学”反应,我们方便地制备了两类基于砜的高代阶非线性光学树枝状大分子,它们具有较高的纯度和令人满意的产率。由于高度支化结构的完美三维(3D)空间隔离以及外部苯环和内部三唑环的隔离效应,这些树枝状大分子表现出高达 181 pm V-1 的大二次谐波系数(d33)值,据我们所知,这是迄今为止含砜基生色团部分的聚合物中的最高值。同时,与硝基生色团类似物相比,由于这些树枝状大分子中的砜基生色团具有较低的偶极矩(μ)和特殊的主链结构,它们的光学透明度和 NLO 稳定性得到了很大程度的提高。