Issue 19, 2016

Extended charge accumulation in ruthenium–4H-imidazole-based black absorbers: a theoretical design concept

Abstract

A theoretical-guided design concept aiming to achieve highly efficient unidirectional charge transfer and multi-charge separation upon successive photoexcitation for light-harvesting dyes in the scope of supramolecular photocatalysts is presented. Four 4H-imidazole–ruthenium(II) complexes incorporating a biimidazole-based electron-donating ligand sphere have been designed based on the well-known 4H-imidazole–ruthenium(II) polypyridyl dyes. The quantum chemical evaluation, performed at the density functional and time-dependent density functional level of theory, revealed extraordinary unidirectional charge transfer bands from the near-infrared to the ultraviolet region of the absorption spectrum upon multi-photoexcitation. Spectro-electrochemical simulations modeling photoexcited intermediates determined the outstanding multi-electron storage capacity for this novel class of black dyes. These remarkable photochemical and photophysical properties are found to be preserved upon site-specific protonation rendering 4H-imidazole–ruthenium(II) biimidazole dyes ideal for light-harvesting applications in the field of solar energy conversion.

Graphical abstract: Extended charge accumulation in ruthenium–4H-imidazole-based black absorbers: a theoretical design concept

Supplementary files

Article information

Article type
Paper
Submitted
09 Feb 2016
Accepted
14 Apr 2016
First published
14 Apr 2016
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2016,18, 13357-13367

Extended charge accumulation in ruthenium–4H-imidazole-based black absorbers: a theoretical design concept

S. Kupfer, Phys. Chem. Chem. Phys., 2016, 18, 13357 DOI: 10.1039/C6CP00911E

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