Spectral and electrochemical studies of bis(diimine)copper(II) complexes in anionic, cationic and nonionic micelles
Spectral and electrochemical studies of bis(diimine)copper(II) complexes in anionic, cationic and nonionic micelles
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DOI：
10.1016/j.jcis.2011.05.075
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发表时间：
2011-10-15
影响因子：
9.9
通讯作者：
Palaniandavar, M.
中科院分区：
文献类型：
--
作者：
Anitha, N.;Balamurugan, R.;Palaniandavar, M.
研究了二亚胺为联吡啶、1，10-菲咯啉、4-甲基-1，10-菲咯啉、5-甲基-1，10-菲咯啉、5-硝基-1，10-菲咯啉的铜（Ⅱ）配合物的光谱和氧化还原行为。4，7-二甲基-1，10-菲咯啉、5，6-二甲基-1，10-菲咯啉、2，9-二甲基-1，10-菲咯啉、3，4，7，8-四甲基-1，10-菲咯啉和双吡啶并-[3，2-d：2 '，3'-f]-喹喔啉在水溶液和SDS、CTAB和Triton X-100胶束水溶液中有显著差异。在水溶液（D2 O）和水胶束的H-1 NMR光谱研究表明，Cu（II）配合物与SDS的相互作用比与CTAB和Triton X-100胶束和在SDS胶束上的网站不同于后者。配体场光谱研究表明，配合物以双阳离子水合形式[Cu（diimine）（2）（H2O）（2）]（2+）存在，并通过库仑力与阴离子SDS胶束发生强烈的相互作用。在Triton X-100和CTAB胶束中，它们以[Cu（diimine）（2）（H2O）Cl]（+）和[Cu（diimine）（2）H-2]的形式存在于疏水微环境中。在胶束微环境中的氧化还原系统的可逆性的实现是显着的，这说明了Cu（II）和Cu（I）物种进行立体化学变化适合于可逆的电子转移。Cu（II）配合物在水溶液和胶束水溶液中的光谱和电化学性质的显着差异说明，配合物主要是依偎在胶束环境中，并意味着，电子转移的配合物的accesselance是不同的，是依赖于胶束的性质以及性质和疏水性的二亚胺配体。(C)2011 Elsevier Inc. All rights reserved.
The spectral and redox behavior of bis(diimine)copper(II) complexes, where diimine is bipyridine, 1, 10-phenanthroline, 4-methyl-1,10-phenanthroline, 5-methyl-1, 10-phenanthroline, 5-nitro-1,10-phenanthroline. 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline and dipyrido-[3,2-d:2',3'-f]-quinoxaline, are significantly different in aqueous and in aqueous SDS, CTAB and Triton X-100 micellar solutions. The H-1 NMR spectral study in aqueous (D2O) and aqueous micelles reveals that the Cu(II) complexes interact more strongly with SDS than with CTAB and Triton X-100 micelles and at sites on SDS micelles different from those on the latter. Ligand Field spectral studies reveal that the complexes exist as the dicationic aquated species [Cu(diimine)(2)(H2O)(2)](2+), which interacts strongly with the anionic SDS micelles through columbic forces. However, they exist as [Cu(diimine)(2)(H2O)Cl](+) and/or [Cu(diimine)(2)H-2] located in the hydrophobic microenvironments in Triton X-100 and CTAB micelles. The attainment of reversibility of the redox systems in the micellar microenvironments is remarkable and this illustrates that the Cu(II) and Cu(I) species undergo stereochemical changes suitable for reversible electron-transfer. The remarkable differences in spectral and electrochemical properties of Cu(II) complexes in aqueous and aqueous micellar solutions illustrate that the complexes are nestled largely within the micellar environments and imply that the accessibilities of the complexes to electron-transfer are different and are dependent on the nature of micelles as well as the nature and hydrophobicity of the diimine ligands. (C) 2011 Elsevier Inc. All rights reserved.