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Dalton Trans. 2008 Sep 28;(36):4846-54. doi: 10.1039/b807526c. Epub 2008 Aug 18.

Synthesis, electrochemical, and molecular inclusion properties of 'canopied' trinuclear ruthenium complexes with six anchoring groups on an ITO electrode.

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Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.


New trinuclear Ru complexes bearing both 1,3,5-tris(2,2':6',2''-terpyridyl)benzene and bis(benzimidazol-2-yl)pyridine with six phosphonate anchors were synthesised and immobilised on an ITO electrode. The 'canopied' structure was proved by AFM measurements. The immobilised Ru trinuclear complex revealed a one step three-electron oxidation process for the Ru(II/III) couple at around +0.9 V vs. Ag/AgCl, indicating that the Ru-Ru interaction is small. For the Ru immobilised ITO surface, the electron transfer blocking and the electron mediation of [Fe(CN)6]4- oxidation through the Ru(III) <--> Ru(II) catalytic cycle are strongly dependent on the alkyl chain length. The spectroelectrochemistry of the Ru trinuclear complex monolayer on the ITO electrode showed a stable electrochromic response under the potential pulse. The present 'canopied' Ru trinuclear complexes hold a small cavity that encapsulates tetrathiafulvalene molecules, which can be proved by a cyclic voltammogram.

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