Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical

0461756 - ÚOCHB 2017 RIV US eng J - Článek v odborném periodiku
Craig, P. R. - Havlas, Zdeněk - Trujillo, M. - Rempala, P. - Kirby, J. P. - Miller, J. R. - Noll, B. C. - Michl, Josef
Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical.
Journal of Physical Chemistry A. Roč. 120, č. 20 (2016), s. 3456-3462. ISSN 1089-5639. E-ISSN 1520-5215
Grant CEP: GA ČR(CZ) GBP208/12/G016
Institucionální podpora: RVO:61388963
Klíčová slova: cyclobutadiene-metal complexes * tetragonal star connectors * square grid polymer * halides
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.847, rok: 2016

Properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative la have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF4- anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and la have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by similar to 0.1 V upon going from 1 to la. Unsuccessful attempts to prepare several other aryl substituted derivatives of 1 by the classical synthetic route are described in the Supporting Information.
Trvalý link: http://hdl.handle.net/11104/0261339