Chemical Functions of Transition Metal Assembled Complexes

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Ito, using infrared spectral lineshape analysis in conjunction with infrared spectroelectrochemistry, determined the rates of intermolecular electron transfer between triruthenium cluster units in mixed valence complexes. The electron transfer rates along a "non symmetric potential energy surface" were elucidated and multiple electron transfer pathways and rates in a bridged cluster trimer were identified. As well as the electronic properties of cluster complexes, methods for assembling extended structures were examined. Using Pt complexes coordinated by high field ligands, strong unsupported Pt->M dative bonds were prepared, and when the Pt complexes were reacted with Ag ion or Rh dimers, linear and large multinuclear complexes were isolated.Sasaki examined two areas: ligand-metal interactions and the synthesis of large complexes. In the first project, the stability of mixed valence states formed by ligand based redox processes were studied, and it was discovered that, when the metal … More centers and ligands mutually form mixed valence states, a "double mixed valence state" exists. In the second area hexanuclear rhenium complexes with new multidentate units were prepared and the structure of a rhenium hexamer having six large pyridylporphyrin ligands was determined.Nishihara's research involved induced structural changes in transition metal complexes. Azo-conjugated transition metal complexes undergo a reversible trans-to-cis isomerization upon concomitant irradiation with a single UV light source and oxidation of the metal. Protonation of a ヲミ-conjugated ferrocene-anthraquinone system caused intermolecular electron transfer to occur. This leads to a novel structural change creating an ヲヌ^6-fulvene-cumulene Fe(II) complex. The structure of the proton attached complex and the properties of the unusually fluxional complex were elucidated.Haga prepared multilayered metal complexes on a solid electrode through layer-by-layer growth. As well, a two-dimensional coordination system was developed at the air-water interface using Langmuir-Blodgett techniques.Fujita furthered his research involving the construction of 2-D and 3-D complexes using 2,4,6-tris(4-pyridyl)triazine as a bridging ligand. An interesting 3-D network, which undergoes a reversible structural change in the solid state upon absorption/desorption of a guest molecule, was prepared. Less