Varying coordination modes of amide ligand in group 12 Hg(II) and Cd(II) complexes: synthesis, crystal structure and nonlinear optical properties

Mobin Shaikh M.; Mishra Veenu; Rai Dhirendra K.; Dota Krithika; Dharmadhikari Aditya K.; Dharmadhikari Jayashree A.; Mathur Deepak; Mathur Pradeep

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Varying coordination modes of amide ligand in group 12 Hg(II) and Cd(II) complexes: synthesis, crystal structure and nonlinear optical properties

机译：12 Hg（II）和Cd（II）配合物中酰胺配体的不同配位模式：合成，晶体结构和非线性光学性质

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Reactions of the amide ligand, H2L (H2L = N, N'-bis[2-(2-pyridyl)methyl]pyridine-2,6-dicarboxamide) with CdCl2 and Hg(CH3COO)(2), in 1 : 1 ratio, at 298 K yield dimeric [Hg(L)](2) (1) and trimeric [Cd-3(H2L)(4)Cl-6] (2), respectively. In 1, the H2L is coordinated to Hg(II) via six N-atoms of central and terminal pyridines as well as of deprotonated amido groups, whereas the carbonyl groups remain free. However, in 2, the H2L is coordinated to Cd(II) through terminal pyridine N atoms and O atoms from carbonyl groups, whereas the nitrogen atoms of the central pyridine, two terminal pyridine and of all amido groups remain free. Molecular structures of 1 and 2 are confirmed by single crystal X-ray studies. The varying coordination modes of H2L give rise to different electrochemical behavior of 1 and 2, which has also been rationalized by theoretical calculations. Moreover, nonlinear optical (NLO) behavior of both complexes has been investigated using ultra-short femtosecond laser pulses, which ensures that the NLO response is exclusively from their electronic component.

机译：酰胺配体H2L（H2L = N，N'-双[2-（2-吡啶基）甲基]吡啶-2,6-二甲苯酰胺）与CdCl2和Hg（CH3COO）（2）的反应比例为1：1 ，在298 K下分别产生二聚体[Hg（L）]（2）（1）和三聚体[Cd-3（H2L）（4）Cl-6]（2）。在图1中，H2L通过中央和末端吡啶以及去质子化酰胺基团的六个N原子与Hg（II）配位，而羰基保持游离。但是，在2中，H2L通过末端吡啶的N原子和羰基的O原子与Cd（II）配位，而中心吡啶，两个末端吡啶和所有酰胺基的氮原子保持游离。 1和2的分子结构已通过单晶X射线研究确定。 H2L的不同配位模式会导致1和2的电化学行为不同，这也已通过理论计算合理化。此外，已经使用超短飞秒激光脉冲研究了两种络合物的非线性光学（NLO）行为，这确保了NLO响应完全来自其电子组件。

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《Dalton transactions: An international journal of inorganic chemistry》 |2015年第4期|共9页
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Mobin Shaikh M.; Mishra Veenu; Rai Dhirendra K.; Dota Krithika; Dharmadhikari Aditya K.; Dharmadhikari Jayashree A.; Mathur Deepak; Mathur Pradeep;
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1. Varying coordination modes of amide ligand in group 12 Hg(II) and Cd(II) complexes: synthesis, crystal structure and nonlinear optical properties [J] . Mobin Shaikh M., Mishra Veenu, Rai Dhirendra K., Dalton transactions: An international journal of inorganic chemistry . 2015,第4期

机译：12 Hg（II）和Cd（II）配合物中酰胺配体的不同配位模式：合成，晶体结构和非线性光学性质
2. Crystal structures and spectral properties of new Cd(II) and Hg(II) complexes of monensic acid with different coordination modes of the ligand [J] . Juliana Ivanova, Ivayla Pantcheva, Mariana Mitewa, Open Chemistry . 2010,第4期

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3. Synthesis, crystal structures and vapor adsorption properties of Hg(II) and Cd(II) coordination polymers derived from two hydrazone Schiff base ligands [J] . Chen Dong-Mei, Wu Xiao-Fan, Liu Yong-Jie, Inorganica Chimica Acta . 2019,第期

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4. Synthesis, Characterization and Third Order Nonlinear Optical Studies of Diimine Based Zn(II), Cd(II) and Hg(II) Complexes [C] . B. J. Rudresha, B. Ramachandra Bhat, K. B. Manjunatha, International Conference on Light . 2011

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Varying coordination modes of amide ligand in group 12 Hg(II) and Cd(II) complexes: synthesis, crystal structure and nonlinear optical properties

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