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镍与一种四齿氨基胍衍生席夫碱配体的分子络合物:结构、光谱和电化学研究以及光电响应。

Ni mol-ecular complex with a tetra-dentate amino-guanidine-derived Schiff base ligand: structural, spectroscopic and electrochemical studies and photoelectric response.

作者信息

Vassilyeva Olga Yu, Buvaylo Elena A, Kokozay Vladimir N, Studzinsky Sergey L, Skelton Brian W, Vasyliev Georgii S

机构信息

Department of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine.

School of Molecular Sciences, M310, University of Western Australia, Perth, WA 6009, Australia.

出版信息

Acta Crystallogr E Crystallogr Commun. 2022 Jan 14;78(Pt 2):173-178. doi: 10.1107/S2056989022000317. eCollection 2022 Jan 1.

Abstract

The new mol-ecular nickel(II) complex, namely, {4-bromo-2-[({'-[(2-oxidobenzylidene)amino]carbamimidoyl}imino)methyl]phenolato}nickel(II) ,-di-methyl-formamide solvate monohydrate, [Ni(CHBrNO)]·CHNO·HO, (I), crystallizes in the triclinic space group with one mol-ecule per asymmetric unit. The guanidine ligand is a product of Schiff base condensation between amino-guanidine, salicyl-aldehyde and 5-bromo-salicyl-aldehyde templated by Ni ions. The chelating ligand mol-ecule is deprotonated at the phenol O atoms and coordinates the metal centre through the two azomethine N and two phenolate O atoms in a -NiNO square-planar configuration [average(Ni-N/O) = 1.8489 Å, angles in the range 83.08 (5)-95.35 (5)°, angles of 177.80 (5) and 178.29 (5)°]. The complex mol-ecule adopts an almost planar conformation. In the crystal, a complicated hydrogen-bonded network is formed through N-H⋯N/O and O-H⋯O inter-molecular inter-actions. Complex (I) was also characterized by FT-IR and H NMR spectroscopy. It undergoes an Ni ↔ Ni redox reaction at = +0.295 V ( Ag/AgCl) in methanol solution. In a thin film with a free surface, complex (I) shows a fast photoelectric response upon exposure to visible light with a maximum photovoltage of ∼178 mV.

摘要

新型分子镍(II)配合物,即{4-溴-2-[({'-[(2-氧化苯亚甲基)氨基]氨基甲脒基}亚氨基)甲基]苯酚根}镍(II),-二甲基甲酰胺溶剂化物一水合物,[Ni(CHBrNO)]·CHNO·HO,(I),结晶于三斜晶系空间群,每个不对称单元中有一个分子。胍配体是氨基胍、水杨醛和5-溴水杨醛在镍离子模板作用下席夫碱缩合的产物。螯合配体分子在酚氧原子处去质子化,并通过两个偶氮甲碱氮原子和两个酚氧原子以-NiNO平面正方形构型配位金属中心[平均(Ni-N/O)=1.8489 Å,角度在83.08(5)-95.35(5)°范围内,角度为177.80(5)和178.29(5)°]。配合物分子采用几乎平面的构象。在晶体中,通过N-H⋯N/O和O-H⋯O分子间相互作用形成了复杂的氢键网络。配合物(I)还通过傅里叶变换红外光谱和核磁共振氢谱进行了表征。它在甲醇溶液中于= +0.295 V(Ag/AgCl)处发生Ni↔Ni氧化还原反应。在具有自由表面的薄膜中,配合物(I)在暴露于可见光时显示出快速的光电响应,最大光电压约为178 mV。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/33b0/8819441/a4153bb9cd1f/e-78-00173-fig1.jpg

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