Syntheses, crystal structures and electronic properties of a series of copper(II) complexes with 3,5-halogen-substituted Schiff base ligands and their solutions
Syntheses, crystal structures and electronic properties of a series of copper(II) complexes with 3,5-halogen-substituted Schiff base ligands and their solutions
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DOI：
10.1016/j.poly.2005.06.018
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发表时间：
2005-12-08
期刊：
影响因子：
2.6
通讯作者：
Einaga, Y
中科院分区：
文献类型：
--
作者：
Akitsu, T;Einaga, Y
系统地研究了10个3，5-卤素取代Schiff碱Cu（II）配合物的结构特征、电子性质、热致结构相变和吸收光谱随溶剂的变化。两个新配合物的结构表征，（N-R-1-苯乙基-和N-R，S-2-丁基-5-溴水杨酰氨基合-κ N-2，O）铜（II），结果表明，它们具有一个压缩的四面体反式[CuN_2O_2]配位几何构型，其中1-苯乙基配合物的trans-N-Cu-N = 159.4（2）度，trans-O-Cu-O = 151.7（3）度，trans-N-Cu-N = 157.9（3）度2-丁基酮的trans-O-Cu-O = 151.0（3）度。所有的配合物在室温下无论其结构如何，在固态加热时都表现出结构相变。10个配合物的吸收光谱表明，d-d带在16000 ~ 20000 cm ~（-1）处有轻微的位移，而pi-pi* 带在24000 ~ 28000 cm ~（-1）处有明显的位移，这表明溶剂的偶极矩可能影响配体的π共轭部分的构象，而不是配位环境.我们还尝试了双（N-R-1-苯乙基-3，5-二氯水杨醛缩氨基-kappa N-2，O）合铜（II）与4-羟基偶氮苯在氯仿溶液中的“光致变色溶质诱导溶剂化变色”。我们成功地观察到对羟基偶氮苯顺反光致异构化引起的配合物吸收光谱中d-d和pi-pi* 带的变化。(c)2005爱思唯尔有限公司保留所有权利。
We have systematically investigated the structural features, electronic properties, thermally-induced structural phase transitions and absorption spectra depending on the solvent for ten Cu(II) complexes with 3,5-halogen-substituted Schiff base ligands. Structural characterization of two new complexes, bis(N-R-1-phenylethyl- and N-R,S-2-butyl-5-bromosalicydenaminato-kappa N-2,O)copper(II), reveals that they afford a compressed tetrahedral trans-[CuN2O2] coordination geometry with trans-N-Cu-N = 159.4(2)degrees and trans-O-Cu-O = 151.7(3)degrees for the 1-phenylethyl complex and trans-N-Cu-N = 157.9(3)degrees and trans-O-Cu-O = 151.0(3)degrees for the 2-butyl one. All the complexes exhibit a structural phase transition by heating in the solid state regardless of their structures at room temperature. The absorption spectra of a series of ten complexes exhibit a slight shift of the d-d band at 1600020 000 cm(-1) and remarkable shift of the pi-pi* band at 24 000-28 000 cm-1, which suggests that the dipole moment of the solvents presumably affects the conformation of the pi-conjugated moieties of the ligands rather than the coordination environment. We have also attempted 'photochromic solute-induced solvatochromism' by a system of bis(N-R-1-phenylethyl-3,5-dichlorosalicydenaminato-kappa N-2,O)copper(II) and photochromic 4-hydroxyazobenzene in chloroform solution. We successfully observed a change of the d-d and pi-pi* bands of the complex in the absorption spectra caused by cis-trans photoisomerization of 4-hydroxyazobenzene. (c) 2005 Elsevier Ltd. All rights reserved.