Simultaneous Occurrence of Three Different Valence Tautomers inmeso-Vinylruthenium-Modified Zinc Porphyrin Radical Cations | Zendy

Jing Chen | Zendy; Evelyn Wuttke | Zendy; Walther Polit | Zendy; Thomas E. Exner | Zendy; Rainer F. Winter | Zendy

Open Access

Simultaneous Occurrence of Three Different Valence Tautomers inmeso-Vinylruthenium-Modified Zinc Porphyrin Radical Cations

Author(s) -

Jing Chen,

Evelyn Wuttke,

Walther Polit,

Thomas E. Exner,

Rainer F. Winter

Publication year - 2013

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja400673c

Subject(s) - chemistry , tautomer , porphyrin , delocalized electron , electron paramagnetic resonance , valence (chemistry) , zinc , redox , photochemistry , radical ion , ground state , valence bond theory , computational chemistry , inorganic chemistry , stereochemistry , molecular orbital , molecule , ion , organic chemistry , nuclear magnetic resonance , atomic physics , physics

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.

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