Synthesis, structure, photochromism and DFT calculations of copper(I)-triphenylphosphine halide complexes of thioalkylazoimidazoles

被引：27

作者：

Saha, Gunomoni ^{[1
]}

Datta, Papia ^{[1
]}

Sarkar, Kamal Krishna ^{[2
]}

Saha, Rajat ^{[3
]}

Mostafa, Golam ^{[3
]}

Sinha, Chittaranjan ^{[1
]}

机构：

[1] Jadavpur Univ, Dept Chem, Inorgan Chem Sect, Kolkata 700032, India

[2] Mahadevananda Mahavidyalaya, Dept Chem, Kolkata 700120, India

[3] Jadavpur Univ, Dept Phys, Kolkata 700032, India

来源：

POLYHEDRON | 2011年 / 30卷 / 04期

关键词：

Copper(I)-thioalkylazoimidazole-halide; X-ray structure; Photochromism; Electrochemistry; DFT computation; EFFECTIVE CORE POTENTIALS; X-RAY-STRUCTURE; MOLECULAR CALCULATIONS; SPECTRAL CHARACTERIZATION; PHOTOISOMERIZATION; ISOMERIZATION; MODULATION; CHEMISTRY;

D O I：

10.1016/j.poly.2010.11.036

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

[Cu(SRaaiNR')(PPh3)X] complexes are synthesized by the reaction of CuX (X = Cl, Br, l), triphenylphosphine and 1-alkyl-2-[(o-thioalkyl)phenylazo]imidazole (SRaaiNR'). The single crystal X-ray structure of [Cu(SEtaaiNH)(PPh3)I] (SEtaaiNH = 2-[(o-thioethyl)phenylazolimidazole) shows a distorted tetrahedral geometry of the copper center with bidentate, N(azo), N(imidazole) chelation of SEtaaiNH and coordination from PPh3 and iodine. These complexes show a trans-to-cis isomerization upon irradiation with UV light. The reverse transformation, cis-to-trans isomerization, is very slow with visible light irradiation and is thermally accessible. The quantum yields (phi(t-c)) of the trans-to-cis isomerization of [Cu(SRaaiNR')(PPh3)X] are lower than the free ligand values. This is due to the increased mass and rotor volume of the complexes compared to the free ligand data. The rate of isomerization follows the order: [Cu (SRaaiNR')(PPh3)Cl] < [Cu(SRaaiNR')(PPh3)Br] < [Cu(SRaaiNR')(PPh3)I]. The activation energy (E-a) of the cis-to-trans isomerization is calculated by a controlled temperature reaction. OFT computation of representative complexes has been used to determine the composition and energy of the molecular levels. (C) 2010 Elsevier Ltd. All rights reserved.

引用

页码：614 / 623

页数：10

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