%0 Journal Article %1 Bubrin.2017 %A Bubrin, Martina %A Paretzki, Alexa %A Huebner, Ralph %A Beyer, Katharina %A Schwederski, Brigitte %A Neugebauer, Petr %A Zalis, Stanislav %A Kaim, Wolfgang. %D 2017 %J Zeitschrift fuer Anorganische und Allgemeine Chemie %K imported %N 21 %P 1621--1627 %R 10.1002/zaac.201700282 %T Probing the Intramolecular Metal-Selenoether Interaction in a Bis(iminosemiquinone)copper(II) Compound %V 643 %X The selenoether compd. Cu(QSeMe)2 H2QSeMe = 4,6-di-tert-butyl-2-(2-methylselenophenyl)aminophenol exhibits solvate-dependent NCuO/OCuN twisting (24° and 33°) and very weak copper-chalcogen interactions (3.30-3.55 \AA) 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.bul.-)-CuII-(Q.bul.-) three-spin system. UV/Vis/NIR spectroelectrochem. in CH2Cl2/0.1 M Bu4NPF6 reveals a broad ligand-to-ligand intervalence charge transfer (Q2- $\rightarrow$ Q.bul.-) band at 1910 nm for the monoanion whereas the stepwise two-electron oxidn. leads to loss of intensity in the near IR region. DFT calcns. of structure, spin d., and electronic transitions were performed to confirm the assignments of oxidn. states and absorption features. on SciFinder(R)

@article{Bubrin.2017, abstract = {The selenoether compd. [Cu(QSeMe)2] [H2QSeMe = 4,6-di-tert-butyl-2-(2-methylselenophenyl)aminophenol] exhibits solvate-dependent NCuO/OCuN twisting (24° and 33°) and very weak copper-chalcogen interactions (3.30-3.55 {\AA}) 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.bul.-)-CuII-(Q.bul.-) three-spin system. UV/Vis/NIR spectroelectrochem. in CH2Cl2/0.1 M Bu4NPF6 reveals a broad ligand-to-ligand intervalence charge transfer (Q2- $\rightarrow$ Q.bul.-) band at 1910 nm for the monoanion whereas the stepwise two-electron oxidn. leads to loss of intensity in the near IR region. DFT calcns. of structure, spin d., and electronic transitions were performed to confirm the assignments of oxidn. states and absorption features. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Bubrin, Martina and Paretzki, Alexa and Huebner, Ralph and Beyer, Katharina and Schwederski, Brigitte and Neugebauer, Petr and Zalis, Stanislav and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/264c076837434e9197c80d2f3d925a862/huebleriac}, doi = {10.1002/zaac.201700282}, interhash = {aa8c275b5735b95b68a20b963d9661f7}, intrahash = {64c076837434e9197c80d2f3d925a862}, issn = {0044-2313}, journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie}, keywords = {imported}, number = 21, pages = {1621--1627}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Probing the Intramolecular Metal-Selenoether Interaction in a Bis(iminosemiquinone)copper(II) Compound}, volume = 643, year = 2017 }