Probing the Intramolecular Metal-Selenoether Interaction in a Bis(iminosemiquinone) copper(II) Compound

0483654 - ÚFCH JH 2018 RIV DE eng J - Článek v odborném periodiku
Bubrin, M. - Paretzki, A. - Hübner, R. - Beyer, K. - Schwederski, B. - Neugebauer, P. - Záliš, Stanislav - Kaim, W.
Probing the Intramolecular Metal-Selenoether Interaction in a Bis(iminosemiquinone) copper(II) Compound.
Zeitschrift für anorganische und allgemeine Chemie. Roč. 643, č. 21 (2017), s. 1621-1627. ISSN 0044-2313. E-ISSN 1521-3749
Grant CEP: GA MŠMT(CZ) LTC17052
Institucionální podpora: RVO:61388955
Klíčová slova: EPR spectroscopy * Molecular structure * Selenium ligand * Spectroelectrochemistry * Copper
Obor OECD: Physical chemistry
Impakt faktor: 1.179, rok: 2017
Způsob publikování: Open access

The selenoether compound [Cu(Q(SeMe))(2)] [H(2)Q(SeMe) = 4,6-di- tert-butyl-2-(2-methylselenophenyl) aminophenol] exhibits solvate-dependent NCuO/OCuN twisting (24 degrees and 33 degrees) and very weak copper-chalcogen interactions (3.30-3.55 angstrom) in the crystal. Structural studies as well as EPR and magnetic measurements confirm a bis(iminosemiquinone) copper(II) configuration with one ligand-based spin in the S = 1/2 ground state. A spin up-down-up sequence is thus inferred for the (Q(center dot-))-Cu-II-(Q(center dot-)) three-spin system. UV/Vis/NIR spectroelectrochemistry in CH2Cl2/0.1 M Bu4NPF6 reveals a broad ligand-to-ligand intervalence charge transfer (Q(2-)> Q(center dot-)) band at 1910 nm for the monoanion whereas the stepwise two-electron oxidation leads to loss of intensity in the near infrared region. DFT calculations of structure, spin density, and electronic transitions were performed to confirm the assignments of oxidation states and absorption features.
Trvalý link: http://hdl.handle.net/11104/0278871