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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Push-pull D-pi-Ru-pi-A chromophores: synthesis and electrochemical, photophysical and second-order nonlinear optical properties
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Push-pull D-pi-Ru-pi-A chromophores: synthesis and electrochemical, photophysical and second-order nonlinear optical properties

机译：推拉D-PI-Ru-PI-A发色团：合成和电化学，光药和二阶非线性光学性能

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摘要

The present work describes the one-pot synthesis and electrochemical, photophysical and second-order nonlinear optical (NLO) properties of a series of dipolar -delocalized Ru(ii) dialkynyl complexes. The eight new asymmetrical D-pi-Ru-pi-A push-pull chromophores incorporate pyranylidene ligands as pro-aromatic donor groups (D) and formaldehyde, indane-1,3-dione, pyrimidine or pyrimidinium as electron-attracting groups (A) separated by ruthenium bis-acetylide fragments and pi-conjugated linkers. The second-order nonlinear optical (NLO) properties of all eight complexes were determined by the Electric-Field-Induced Second Harmonic generation (EFISH) technique (operating at 1907 nm), and were compared to those of their purely organic analogs. All investigated compounds (organic and organometallic) exhibited positive mu beta values, which dramatically increased for the complexes due to the presence of ruthenium in the pi-conjugated core. The second-order NLO response could also be easily modulated by changing the nature of alkynyl substituents. The most promising ruthenium complexes 7 and 8 of the series with the pyrimidinium fragment displayed mu beta values of 14000 x 10(-48) esu. The effect of structural modifications on the redox and spectroscopic properties of the complexes was also studied. The intramolecular charge transfer (ICT) occurring through the ruthenium center of the push-pull sigma-dialkynyl complexes was investigated by combining experimental and theoretical data.
机译：本作者描述了一系列偶极定位的Ru（II）二酮二极化ru（II）二极基络合物的单盆合成和电化学，光物理和二阶非线性光学（NLO）性质。八个新的不对称D-Pi-Ru-Pi-a推拉式发色团掺入吡喃基亚乙烯配体作为促芳族供体基团（D）和甲醛，吲哚-1,3-二酮，嘧啶或嘧啶为电子吸引基团（a ）由钌双 - 乙炔片碎片和PI-缀合的接头分离。所有八个复合物的二阶非线性光学（NLO）性质由电场诱导的二次谐波产生（海蜇）技术（在1907nm处运行）确定，并与它们纯有机类似物的相比。所有所研究的化合物（有机体和有机金属）表现出阳性β值，由于在PI缀合的芯中存在钌的存在，络合物显着增加。通过改变炔基取代基的性质，还可以容易地调节二阶NLO响应。与嘧啶碎片的系列中最有前途的钌配合物7和8显示MUβ值14000×10（-48）eSU。还研究了结构修饰对复合物的氧化还原和光谱性质的影响。通过组合实验和理论数据来研究通过推挽Σ-Digkynyls络合物的钌中心发生的分子内电荷转移（ICT）。

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