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Issue 35, 2011
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The effect of the position of methyl substituents on photophysical and photochemical properties of [Ru(x,x′-dmb)(CN)4]2 complexes: experimental confirmation of the theoretical predictions

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Abstract

The molecular geometry, electronic structure and electronic spectra and the energy levels of the molecular orbitals responsible for the photophysical characteristics of a series of solvent tunable [Ru(x,x′-dmb)(CN)4]2 complexes (where x,x′-dmb = x,x′-dimethyl-2,2′-bipyridine) were calculated by density-functional theory-based quantum chemical methods, with the purpose of proposing for experimental study the best candidate for sensitizing electron- and energy transfer processes or for light induced structural changes in the molecule. The methods applied include geometry optimization using the B3LYP functional combination and various basis sets, time-dependent density functional theory with the B3LYP and PBE0 functionals, with and without explicit inclusion of coordinated solvent H2O molecules and the conductor-like polarizable continuum model for solvation. The accuracy of the theoretical predictions was tested by experiments: the model compounds have been synthesized and characterized by various spectroscopic methods, such as 1H-NMR, UV-Vis absorption and emission spectroscopy and by cyclic voltammetry. Excellent correlation was found between the theoretically calculated and the experimentally determined photophysical and photochemical characteristics. The electronic transition energies measured in water are superbly reproduced by TD-PBE0 and well by TD-B3LYP, but the performance of both functionals is worse if the solvent is acetonitrile.

Graphical abstract: The effect of the position of methyl substituents on photophysical and photochemical properties of [Ru(x,x′-dmb)(CN)4]2− complexes: experimental confirmation of the theoretical predictions

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Publication details

The article was received on 05 Apr 2011, accepted on 13 Jul 2011 and first published on 08 Aug 2011


Article type: Paper
DOI: 10.1039/C1CP21052A
Phys. Chem. Chem. Phys., 2011,13, 16033-16045

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    The effect of the position of methyl substituents on photophysical and photochemical properties of [Ru(x,x′-dmb)(CN)4]2 complexes: experimental confirmation of the theoretical predictions

    P. Szabó, G. Lendvay, A. Horváth and M. Kovács, Phys. Chem. Chem. Phys., 2011, 13, 16033
    DOI: 10.1039/C1CP21052A

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