title: Simultaneous occurrence of three different valence tautomers in meso-vinylruthenium-modified zinc porphyrin radical cations.
abstract: The mixed-valent radical cation of a styrylruthenium-modified meso-tetraarylzinc porphyrin forms a mixture of three different valence tautomers (VTs) in CH2Cl2 or 1,2-C2H4Cl2 solutions. One of these VTs has the charge and spin delocalized over the porphyrin and the styrylruthenium moieties, while the other two display charge and spin localization on just one of the different redox sites. The relative amounts of the three different VTs were determined by EPR and IR spectroscopies at variable temperatures, while delocalization in the ground state was confirmed by DFT calculations.
authors: Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78457 Konstanz, Germany.
authors: Jing
authors: J
authors: Chen
authors: Evelyn
authors: E
authors: Wuttke
authors: Walther
authors: W
authors: Polit
authors: Thomas
authors: T
authors: Exner
authors: Rainer F
authors: RF
authors: Winter
mesh_terms: D002412:Cations / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013343:Styrenes / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D002412:Cations; D005609:Free Radicals; D008665:Metalloporphyrins; D009942:Organometallic Compounds; D013343:Styrenes; D012428:Ruthenium; D015032:Zinc