A Computational Analysis of the Intrinsic Plasticity of Five-Coordinate Cu(II) Complexes and the Factors Leading to the Breakdown of the Orbital Directing Effect in Paddlewheel Secondary Building Units

A Computational Analysis of the Intrinsic Plasticity of Five-Coordinate Cu(II) Complexes and the Factors Leading to the Breakdown of the Orbital Directing Effect in Paddlewheel Secondary Building Units

© 2019 Wiley Periodicals, Inc.

Détails bibliographiques
Publié dans:Journal of computational chemistry. - 1984. - 41(2020), 4 vom: 05. Feb., Seite 340-348
Auteur principal: Alzahrani, Khalid A H (Auteur)
Autres auteurs: Deeth, Robert J
Format: Article en ligne
Langue:English
Publié: 2020
Accès à la collection:Journal of computational chemistry
Sujets:Journal Article copper paddlewheel flexible MOFs orbital directing effect quantum chemical calculations
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520 |a Quantum chemical calculations on model copper paddlewheel (CPW) complexes of general formula [Cu2 (μ2 -O2 CR)4 L2 ] establish two local coordination geometries at the metal centers depending on the balance between equatorial and axial ligand fields. When the equatorial field is stronger than the axial field (large ligand field asymmetry), d x 2 - y 2 dominates the stereochemical activity of the d9 shell resulting in a relatively rigid, "orbitally directed" planar or square pyramidal structure. However, if the axial field is significantly increased, or the equatorial field moderately weakened, a small ligand field asymmetry results and both d x 2 - y 2 and d z 2 are involved in the stereochemical activity. This results in a "plastic," distorted trigonal bipyramidal geometry where the former axial ligand moves into one of the original four equatorial positions. Linkers already used to synthesize zinc-dabco MOFs (dabco = 1,4-diazabicyclo[2.2.2]octane) are shown to generate plastic CPW secondary building unit analogs with potential implications for conferring breathing behavior for MOFs which would currently be assumed to be rigid. © 2019 Wiley Periodicals, Inc 
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