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Diradical Bis‐o‐iminosemiquinonato Zinc Complex: Spectroscopy, Magneto‐ and Electrochemistry
Author(s) -
Poddel'sky A. I.,
Smolyaninov I. V.,
Skatova A. A.,
Lukoyanov A. N.,
Fukin G. K.,
Berberova N. T.,
Cherkasov V. K.,
Abakumov G. A.
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700596
Subject(s) - diradical , zinc , electron paramagnetic resonance , chemistry , crystallography , electrochemistry , antiferromagnetism , spectroscopy , ground state , electron transfer , redox , magnetic susceptibility , infrared spectroscopy , ligand (biochemistry) , inorganic chemistry , photochemistry , nuclear magnetic resonance , condensed matter physics , physics , organic chemistry , atomic physics , excited state , electrode , quantum mechanics , singlet state , biochemistry , receptor
Bis‐ o ‐iminobenzosemiquinonato zinc and cadmium complexes M(ISQ‐Pr i ) 2 (M = Zn, 1 ; M = Cd, 2 ) were found to be diradical complexes of a distorted tetrahedral geometry according to X‐band EPR spectroscopy. Tetrahedral structure of zinc complex 1 was confirmed by X‐ray diffraction analysis. The spectro‐ and electrochemistry of zinc complex 1 have been studied in details. For 1 a series of reversible one‐electron‐transfer waves leads to the formation of the anions and cations [M(L) 2 ] 2−,1−,1+,2+ . All redox processes were shown to be ligand‐based. From variable temperature magnetic susceptibility measurements it has been established that at room temperature 1 possesses an S = 1 state with weak antiferromagnetic coupling between radical ligands ( J = −41.4±0.4 cm −1 ) leading to an S = 0 ground state at low temperature.