title: Realization of SOMO-HOMO level conversion for a TEMPO-dithiolate ligand by coordination to platinum(II).
abstract: We developed a TEMPO-bound dithiolate ligand (= tempodt) and its Pt(diimine)(dithiolate) complex to realize a unique electronic structure with the potential for unprecedented functionalities. The physical properties and electronic structures of tempodt, (tempodt)Pt, and their related compounds were investigated by cyclic voltammetry, UV-visible spectroscopy, electron spin resonance (ESR) spectroscopy, and other techniques. It was revealed that (tempodt)Pt showed an unusual electronic structure in which the HOMO level (= pi-conjugated dithiolate-based orbital) was located above the SOMO level attributed to the TEMPO moiety, and that this situation was achieved via a drastic electronic structure change of SOMO-HOMO level conversion through complex formation. These findings were further supported by an investigation into a one-electron oxidized (tempodt)Pt and related complexes.
authors.affiliation: Department of Chemistry, Graduate School of Science, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Kusamoto
authors.forename: Shoko
authors.initials: S
authors.lastname: Kume
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishihara
mesh_terms: D018360:Crystallography, X-Ray; D003497:Cyclic N-Oxides / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D010984:Platinum / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D003497:Cyclic N-Oxides; D005609:Free Radicals; D008024:Ligands; D009944:Organoplatinum Compounds; D013438:Sulfhydryl Compounds; D010984:Platinum; C003959:TEMPO