Second-Order NLO Switches from Molecules to Polymer Films Based on Photochromic Cyclometalated Platinum(II) Complexes
Second-Order NLO Switches from Molecules to Polymer Films Based on Photochromic Cyclometalated Platinum(II) Complexes
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DOI：
10.1021/ja4131615
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发表时间：
2014-04-09
影响因子：
15
通讯作者：
De Angelis, Roberta
中科院分区：
文献类型：
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作者：
Boixel, Julien;Guerchais, Veronique;De Angelis, Roberta
新型光致变色二噻吩基乙烯基铂（II）配合物。制备并表征了（（CNN）-N-boolean AND-N-boolean AND）Pt（C6 C-DTE-C6 H4-D）（（（CNN）-N-boolean AND-N-boolean AND）= 4，4 ′-二（正己基）-6-苯基-2，2 ′-联吡啶; D = H，NMe 2）。其优异的光致变色性能允许其二阶非线性光学性质在溶液中的光诱导开关，如通过EFISH技术测量的，由于在适当的电磁辐射后形成扩展的π共轭配体。深入了解的电子结构的配合物和它们的激发态的性质已经得到了DFT和TD-DFT计算。这些新的Pt（II）配合物被纳米组织在聚合物薄膜被极化，提供新的材料，其特征在于良好的二阶非线性光学响应，可以很容易地切换，具有良好的非线性光学对比度。据我们所知，我们的化合物允许设计基于金属络合物的可切换NLO聚合物膜的第一个例子。
Novel photochromic dithienylethene-based platinum(II) complexes.((CNN)-N-boolean AND-N-boolean AND)Pt(C C-DTE-C6H4-D) (((CNN)-N-boolean AND-N-boolean AND) = 4,4'-di(n-hexyl)-6-phenyl-2,2'-bipyridine; D = H, NMe2) were prepared and characterized. Their excellent photochromic properties allow the photoinduced switching of their second-order nonlinear optical properties in solution, as measured by the EFISH technique, due to formation of an extended pi-conjugated ligand upon suitable electromagnetic radiation. Insights into the electronic structures of the complexes and the nature of their excited states have been obtained by DFT and TD-DFT calculations. These novel Pt(II) complexes were nanoorganized in polymer films which were poled, affording new materials characterized by a good second-order NLO response that can be easily switched, with an excellent NLO contrast. To the best of our knowledge, our compounds allowed designing the very first examples of switchable NLO polymer films based on metal complexes.