Second-Order NLO Switches from Molecules to Polymer Films Based on Photochromic Cyclometalated Platinum(II) Complexes

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• 作者：Julien Boixel ; V茅ronique Guerchais ; Hubert Le Bozec ; Denis Jacquemin ; Anissa Amar ; Abdou Boucekkine ; Alessia Colombo ; Claudia Dragonetti ; Daniele Marinotto ; Dominique Roberto ; Stefania Righetto ; Roberta De Angelis
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：April 9, 2014
• 年：2014
• 卷：136
• 期：14
• 页码：5367-5375
• 全文大小：459K
• 年卷期：v.136,no.14(April 9, 2014)
• ISSN：1520-5126

文摘

Novel photochromic dithienylethene-based platinum(II) complexes (CNN)Pt(C鈮鈥擠TE鈥擟₆H₄鈥擠) ((CNN) = 4,4鈥?di(n-hexyl)-6-phenyl-2,2鈥?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 蟺-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.