Strong Dipolar Effects on an Octupolar Luminiscent Chromophore: Implications on their Linear and Nonlinear Optical Properties

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• 作者：Arturo Jiménez-Sánchez ; Itzel Isunza-Manrique ; Gabriel Ramos-Ortiz ; Jesús Rodríguez-Romero ; Norberto Farfán ; Rosa Santillan
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：June 30, 2016
• 年：2016
• 卷：120
• 期：25
• 页码：4314-4324
• 全文大小：689K
• 年卷期：0
• ISSN：1520-5215

文摘

Design parameters derived from structure–property relationships play a very important role in the development of efficient molecular-based functional materials with optical properties. Here, we report on the linear and nonlinear optical properties of a fluorene-derived dipolar system (DS) and its octupolar analogue (OS), in which donor and acceptor groups are connected by a phenylacetylene linkage, as a strategy to increase the number of delocalized electrons in the π-conjugated system. The optical nonlinear response was analyzed in detail by experimental and theoretical methods, showing that, in the octupolar system OS, the dipolar effects induced a strong two-photon absorption process whose magnitude is as large as 2210 GM at infrared wavelengths. Solvatochromism studies were implemented to obtain further insight on the charge transfer process. We found that the triple bond plays a fundamental role in the linear and nonlinear optical responses. The strong solvatochromism behavior in DS and OS was analyzed by using four empirical solvent scales, namely Lippert–Mataga, Kamlet–Taft, Catalán, and the recently proposed scale of Laurence et al., finding consistent results of strong solvent polarizability and viscosity dependence. Finally, the role of the acceptor groups was further studied by synthesizing the analogous compound 2DS, having no acceptor group.