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离散二聚体铜(II)配合物到离散四聚体铜(II)配合物的气相扩散介导的单晶到单晶转变

Vapor-diffusion-mediated single crystal-to-single crystal transformation of a discrete dimeric copper(II) complex to a discrete tetrameric copper(II) complex.

作者信息

Mobin Shaikh M, Srivastava Ashwini K, Mathur Pradeep, Lahiri Goutam Kumar

机构信息

National Single Crystal X-ray Diffraction Facility and Department of Chemistry, IIT Bombay, Powai, Mumbai 400076, India.

出版信息

Inorg Chem. 2009 Jun 1;48(11):4652-4. doi: 10.1021/ic900510v.

Abstract

The symmetric dimeric complex Cu(mu(2)-hep)(TFA)(H(2)O) (1) has been synthesized from 2-(2-hydroxyethyl)pyridine (hep-H), trifluoroacetic acid (TFA-H), and copper acetate in a 95:5 (v/v) MeOH-H(2)O mixture at 298 K. Each Cu(II) ion in 1 is linked with two mu(2)-alcoholic oxygen atoms and one pyridine nitrogen atom of hep, and the other two coordination sites are occupied by the oxygen donors of TFA and H(2)O. At room temperature, the blue single crystals of 1 transform to the green single crystals of a tetrameric complex, [Cu(4)(mu(3)-hep)(2)(mu(2)-hep)(2)(mu(2)-TFA)(2)(TFA)(2)] (2), in presence of alcoholic vapor. The facile single crystal-to-single crystal (SCSC) transformation of 1 to 2 is accompanied by the removal of coordinated H(2)O molecules in 1 and concomitant formation of four new covalent bonds, two Cu-O(mu(3)-hep) and two Cu-O(mu(2)-TFA). The SCSC transformation of 1 to 2 is selective to the alcoholic vapor; the exposure of single crystals of 1 to heat or light or in vacuum has resulted in an immediate loss in crystallinity.

摘要

对称二聚体配合物[Cu(μ₂ - hep)(TFA)(H₂O)]₂ (1) 是由2-(2-羟乙基)吡啶(hep - H)、三氟乙酸(TFA - H)和醋酸铜在95:5 (v/v) 的甲醇 - H₂O混合溶剂中于298 K合成的。配合物1中的每个Cu(II)离子与两个μ₂ - 醇羟基氧原子和一个hep的吡啶氮原子相连,另外两个配位点被TFA和H₂O的氧供体占据。室温下,配合物1的蓝色单晶在酒精蒸汽存在下转变为四聚体配合物[Cu₄(μ₃ - hep)₂(μ₂ - hep)₂(μ₂ - TFA)₂(TFA)₂] (2) 的绿色单晶。配合物1到2的这种容易的单晶到单晶(SCSC)转变伴随着配合物1中配位水分子的去除以及同时形成四个新的共价键,即两个Cu - O(μ₃ - hep)和两个Cu - O(μ₂ - TFA)。配合物1到2的SCSC转变对酒精蒸汽具有选择性;将配合物1的单晶暴露于热、光或真空中会导致其立即失去结晶性。

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