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硫氰酸盐介导的12族金属离子基于苯酚的“端基封闭”分隔配体配合物的结构多样性:对其光物理性质和类磷酸酶活性的研究

Thiocyanate mediated structural diversity in phenol based "end-off" compartmental ligand complexes of group 12 metal ions: Studies on their photophysical properties and phosphatase like activity.

作者信息

Adhikary Jaydeep, Chakraborty Prateeti, Samanta Sugata, Zangrando Ennio, Ghosh Sanjib, Das Debasis

机构信息

Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700 009, India; Department of Chemical Sciences, Ariel University, Ariel 40700, Israel.

Department of Chemistry, School of Basic Sciences and Research, Sharda University, Greater Noida, Uttar Pradesh 201306, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2017 May 5;178:114-124. doi: 10.1016/j.saa.2017.01.041. Epub 2017 Jan 25.

Abstract

The reaction of a pentadentate compartmental ligand LH, namely 4-tert-Butyl-2,6-bis-[(2-pyridin-2-yl-ethylimino)-methyl]-phenol, with group 12 metal ions (Zn, Cd, Hg) followed by addition of NaSCN afforded one discrete dinuclear complex Zn(L)(SCN), and two polymeric 1D species [Cd(L)(SCN)(AcO)] (2) and [Hg(L)(SCN)] (3). All the complexes have been structurally characterized by single crystal X-ray diffraction. The crystal structure of the complexes reveals different coordination modes of thiocyanate anion that affect the different topology detected in the compounds: the anions are μ-NCS and μ-NCS connected in complex 1, while μ-NCS bridging mode is observed in 2, and μ-SCN and μ-NCS in 3. The polymeric Hg complex of the bicompartmental ligand system here reported is unprecedented. Detail study of their photophysical properties including the phosphorescence spectra at 77K has been done. Phosphatase like activity of all the three complexes has been performed in DMSO-HO medium and their activity follows the order of 1>2>>3.

摘要

五齿隔室配体LH,即4-叔丁基-2,6-双[(2-吡啶-2-基-乙基亚氨基)-甲基]-苯酚,与第12族金属离子(锌、镉、汞)反应,随后加入硫氰酸钠,得到一种离散的双核配合物[Zn(L)(SCN)](1),以及两种聚合物一维物种[Cd(L)(SCN)(AcO)](2)和[Hg(L)(SCN)](3)。所有配合物均通过单晶X射线衍射进行了结构表征。配合物的晶体结构揭示了硫氰酸根阴离子的不同配位模式,这影响了化合物中检测到的不同拓扑结构:在配合物1中阴离子为μ-NCS和μ-NCS相连,而在2中观察到μ-NCS桥连模式,在3中为μ-SCN和μ-NCS。本文报道的双隔室配体体系的聚合物汞配合物是前所未有的。已对其光物理性质进行了详细研究,包括77K下的磷光光谱。在二甲基亚砜-水介质中对所有三种配合物的磷酸酶样活性进行了测试,其活性顺序为1>2>>3。

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