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Int. J. Mol. Sci. 2015, 16(2), 3955-3969;

Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Author to whom correspondence should be addressed.
Academic Editor: John George Hardy
Received: 15 January 2015 / Revised: 27 January 2015 / Accepted: 5 February 2015 / Published: 12 February 2015
(This article belongs to the Special Issue Supramolecular Interactions)
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We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO2 in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions. View Full-Text
Keywords: Schiff base complexes; copper(II) complexes; UV–Vis spectra; TD-DFT; TiO2 Schiff base complexes; copper(II) complexes; UV–Vis spectra; TD-DFT; TiO2

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Takeshita, Y.; Takakura, K.; Akitsu, T. Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2. Int. J. Mol. Sci. 2015, 16, 3955-3969.

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