title: Site-specific synthesis of oxo-bridged mixed-valence binuclear complexes on mesoporous silica.
abstract: We report the site-specific synthesis of mixed valence TiIV-O-FeII complexes within the pores of ordered mesoporous silica (SBA-15). By using 6-di- tert-butylpyridine as the selective activator of tripodally linked TiIV-OH groups of Ti-grafted SBA-15, the FeCl2.4H2O complexes reacted selectively with the nucleophilic TiIV-O(-) groups. The formation of Si-O-FeII byproducts, due to the reaction with the abundant Si-OH groups, was successfully restricted and the selectivity for forming the TiIV-O-FeII complexes exceeded 80%. The metal-metal interaction of TiIV-O-FeII complexes was confirmed by the appearance of TiIV/FeII --> TiIII/Fe III metal-to-metal charge transfer band, and their coordination, valency, and spin state were characterized by diffuse transmission UV-vis, Fourier transform IR, and Fe K-edge X-ray absorption fine structure measurements. It was also confirmed that the present methods can be extended to other metal combinations of TiIV-O-NiII and TiIV-O-MnII. The electron transfer processes occurring under photoinduced metal-to-metal charge transfer of oxo-bridged mixed valence complexes on silica supports have recently been proven as a new class of visible-light-sensitive redox centers. Thus, the present synthetic procedure allows the fabrication of a variety of photochemical reaction centers according to the molecular-level design.
authors.affiliation: Department of Applied Chemistry, School of Engineering, the University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Okamoto
authors.forename: Ryuhei
authors.initials: R
authors.lastname: Nakamura
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Osawa
authors.forename: Kazuhito
authors.initials: K
authors.lastname: Hashimoto