title: Heterometallic one-dimensional chain with tetradeca metal repetition constructed by amidate bridged dirhodium and pivalate bridged diplatinum complexes influenced by hydrogen bonding.
abstract: A novel heterometallic one-dimensional (1-D) chain complex, [{Rh2(acam)4}3{Pt2(OPiv)2(NH3)4}4](ClO4)8 (4, acam = acetamidate, OPiv = pivalate), has been synthesized and characterized by single-crystal X-ray analysis and diffuse reflectance spectroscopy. Complex 4 comprises [Rh2(acam)4] (i.e. [Rh2]) and [Pt2(OPiv)2(NH3)4](ClO4)2 (i.e. [Pt2]), where Rh and Pt atoms are axially linked by metal-metal bonds with a repetition of -{[Rh2]-[Pt2]-[Rh2]-[Pt2]-[Rh2]-[Pt2]-[Pt2]}n-. All metal oxidation states in 4, determined by structural and X-ray photoelectron spectral analyses, are +2. The unbridged Rh-Pt and Pt-Pt bonds in 4 are supported by multiple hydrogen bonds; the distances of Rh-Pt bonds are relatively longer than those in previously reported 1-D chains despite smaller torsion angles between the Rh and Pt coordination planes. Diffuse reflectance spectra revealed that the electronic structure of 4 has a larger gap between filled and vacant σ-type orbitals and a smaller gap between a filled π*(Rh2) and a vacant σ-type orbital.
authors.affiliation: Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido 1-1, Gifu, 501-1193, Japan. k_uemura@gifu-u.ac.jp.
authors.forename: Tomofumi
authors.initials: T
authors.lastname: Yamada
authors.affiliation: Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido 1-1, Gifu, 501-1193, Japan. k_uemura@gifu-u.ac.jp.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Ebihara
authors.affiliation: Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido 1-1, Gifu, 501-1193, Japan. k_uemura@gifu-u.ac.jp.
authors.forename: Kazuhiro
authors.initials: K
authors.lastname: Uemura