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A Synergetic Experimental and Computational Approach Towards a Better Comprehension of Redox Reactions of N3 Dye [cis‐bis(Isothiocyanato)‐Ruthenium(II)‐bis(2, 2’‐Bipyridine‐4,4’‐Dicarboxylic Acid] in Solution
Author(s) -
Zerón Paulino,
CarmonaEspíndola Javier,
FloresLeonar Martha M.,
Gázquez José L.,
González Ignacio,
AmadorBedolla Carlos,
UgaldeSaldívar Víctor M.
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201800716
Subject(s) - ruthenium , redox , chemistry , time dependent density functional theory , bipyridine , photochemistry , 2,2' bipyridine , electron paramagnetic resonance , computational chemistry , inorganic chemistry , catalysis , crystallography , organic chemistry , density functional theory , physics , nuclear magnetic resonance , crystal structure
Charge transfer processes in coordination compounds with labile ligands are strongly dependent on the coordination sphere. Various intermediate steps involve creation of new species during the redox reactions in solution. For the prototypical N3 dye [cis–bis(isothiocyanato)‐ruthenium(II)‐bis(2, 2’‐bipyridine‐4,4’‐dicarboxylic acid], its electro‐oxidation transformation involves a knotty mechanism in which the coordination of the Ru(II) with SCN ‐ ligands is modified. This process produces reactive chemical species that are not easily identified during the spectroelectrochemical characterization. TDDFT calculated absorption spectra were used as an easy and trustworthy tool to identify actual intermediates amongst different possible products in coordination compound transformation. The evolution of the spectra demonstrates, by an experimental and theoretical synergetic approach, the complicated reaction processes, and allows the identification of intermediate and final species both in DMSO and THF solvents. By combining EPR/UV‐Vis spectroscopies and TDDFT calculations we show previously undetected Ru(III) species in the N3 dye at higher potentials in both solvents.