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

Péter Szabó, G. Lendvay, Attila Horváth, Margit Kovács

Research output: Article

1 Citation (Scopus)

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.

Original languageEnglish
Pages (from-to)16033-16045
Number of pages13
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number35
DOIs
Publication statusPublished - szept. 21 2011

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functionals
Density functional theory
predictions
density functional theory
sensitizing
Molecules
Geometry
Solvation
Emission spectroscopy
Molecular orbitals
geometry
Ultraviolet spectroscopy
Absorption spectroscopy
electronic spectra
Energy transfer
Electron energy levels
Cyclic voltammetry
acetonitrile
Electronic structure
solvation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

@article{7675246dcde7411998fe280f8df69a2f,
title = "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",
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.",
author = "P{\'e}ter Szab{\'o} and G. Lendvay and Attila Horv{\'a}th and Margit Kov{\'a}cs",
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T1 - The effect of the position of methyl substituents on photophysical and photochemical properties of [Ru(x,x′-dmb)(CN)4]2- complexes

T2 - Experimental confirmation of the theoretical predictions

AU - Szabó, Péter

AU - Lendvay, G.

AU - Horváth, Attila

AU - Kovács, Margit

PY - 2011/9/21

Y1 - 2011/9/21

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AB - 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.

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