Electrochemical, Linear Optical, and Nonlinear Optical Properties and Interpretation by Density Functional Theory Calculations of (4-N,N-Dimethylaminostyryl)-Pyridinium Pendant Group Associated

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• 作者：Frdric Dumur ; Cdric R. Mayer ; Khuyen Hoang-Thi ; Isabelle Ledoux-Rak ; Fabien Miomandre ; Gilles Clavier ; Eddy Dumas ; Rachel Mallet-Renault ; Michel Frigoli ; Joseph Zyss ; Francis Scheresse
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：September 7, 2009
• 年：2009
• 卷：48
• 期：17
• 页码：8120-8133
• 全文大小：1077K
• 年卷期：v.48,no.17(September 7, 2009)
• ISSN：1520-510X

文摘

The synthesis, linear optical and nonlinear optical properties, as well as the electrochemical behavior of a series of pro-ligands containing the 4-(4-N,N-dimethylaminostyryl)-1-methyl pyridinium (DASP⁺) group as a push−pull moiety covalently linked to terpyridine or bipyridine as chelating ligands are reported in this full paper. The corresponding multifunctional Ru^II and Zn^II complexes were prepared and investigated. The structural, electronic, and optical properties of the pro-ligands and the ruthenium complexes were investigated using density functional theory (DFT) and time-dependent (TD) DFT calculations. A fairly good agreement was observed between the experimental and the calculated electronic spectra of the pro-ligands and their corresponding ruthenium complexes. A quenching of luminescence was evidenced in all ruthenium complexes compared with the free pro-ligands but even the terpyridine-functionalized metal complexes exhibited detectable luminescence at room temperature. Second order nonlinear optical (NLO) measurements were performed by Harmonic Light Scattering and the contribution of the DASP⁺ moieties (and their relative ordering) and the metal-polypyridyl core need to be considered to explain the nonlinear optical properties of the metal complexes.