jp400193k_si_001.pdf (1.67 MB)
Redox State Sensitive Spectroscopy of the Model Compound [(H-dcbpy)2RuII(NCS)2]2– (dcbpy = 2,2′-Bipyridine-4,4′-dicarboxylato)
journal contribution
posted on 2016-02-19, 13:57 authored by Linda Zedler, Julien Guthmuller, Inês Rabelo de Moraes, Sven Krieck, Michael Schmitt, Jürgen Popp, Benjamin DietzekThe charge transfer reaction mechanism
in a ruthenium polypyridine
model complex with isothiocyanato ligands, i.e., [(H-dcbpy)2Ru(NCS)2]2– 2Bu4N+ (Ru2H) (dcbpy = 2,2′-bipyridine-4,4′-dicarboxylato),
has been investigated by combining UV–vis absorption, resonance
Raman spectroscopy, and electrochemical methods. Understanding the
photophysics of light-harvesting complexes of this class is an indispensable
prerequisite to improve the efficiency and durability of photocatalysts
for hydrogen production, a possible basis of future energy sources.
In this study, light-induced excitation of Ru2H has been mimicked
by electrochemical reduction, and the intermediate redox state has
been extensively characterized by UV–vis absorption and resonance
Raman spectroscopy. The reduction occurs at the dcbpy ligand, and
the spectra of reduced Ru2H resemble the excited state spectra. The
reduced Ru2H exhibits a new absorption band at 440 nm localized at
the bipyridine framework. This assignment is consistent with the observed
enhancement of the bipyridine bands with respect to nonreduced Ru2H
in the resonance Raman spectra of the reduced Ru2H excited at 458
nm. The detected shifts in Raman band positions and changes in the
relative band intensities between nonreduced and reduced Ru2H are
rationalized on an orbital level by quantum chemical calculations.
The results indicate that the reduction is accompanied by deprotonation,
i.e., an intramolecular electron-transfer-induced cleavage of the
O–H bond splitting off hydrogen, of the carboxylic acid groups
of the dcbpy ligand.