Theoretical Study of Specific Solvent Effects on the Optical and Magnetic Properties of Copper(II) Acetylacetonate
2011 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 115, no 8, 1331-1339 p.Article in journal (Refereed) Published
Specific and basicity solvent effects on the visible near-infrared electronic transitions and the electron paramagnetic resonance (EPR) parameters of the copper(II) acetylacetonate complex, Cu(acac)(2), have been investigated at the density functional theory level. The computed absorption transitions as well as the EPR parameters show a strong dependence on the direct coordination environment around the Cu(II) complex. High solvatocromic shifts are observed for 3d-3d transitions, with the highest effect observed for the d(z2)-->d(xy) transition, which is red-shifted by 6000 cm(-1) and 9000 cm(-1) in water and pyridine solvent models, respectively. Compared to the electronic g-tensors, the hyperfine coupling constants of the Cu(acac)(2) complex show a more pronounced dependence on the effect of base strength of solvent. Overall, the present methodology satisfactorily models the solvent effect on the optical and magnetic properties of the Cu(acac)(2) complex, and theory and experiment agree sufficiently well to warrant the use of the computed optical and EPR parameters to elucidate the coordination environment of the Cu(II) systems in basic solutions.
Place, publisher, year, edition, pages
2011. Vol. 115, no 8, 1331-1339 p.
DENSITY-FUNCTIONAL THEORY, TRANSITION-METAL-COMPLEXES, KOHN-SHAM THEORY, EPR PARAMETERS, ABSORPTION-SPECTRA, DFT CALCULATIONS, AQUA COMPLEXES, BASIS-SET, PREDICTION, EXCHANGE
IdentifiersURN: urn:nbn:se:kth:diva-31326DOI: 10.1021/jp109826pISI: 000287636400004ScopusID: 2-s2.0-79952018281OAI: oai:DiVA.org:kth-31326DiVA: diva2:404686
FunderSwedish e‐Science Research Center
QC 20110318 Denna artikel är en förändrad version av manuskriptet "Theoretical study of specific solvent effects on the optical and magnetic properties of copper(II) acetylacetonate" som hör till avhandlingen "Optical and Magnetic Properties of Copper(II) Compounds".2011-03-182011-03-142012-05-23Bibliographically approved