The charge transfer reaction mechanism in functional Ruthenium polypyridine complexes used for solar-energy conversion are studied by combining UV-Vis absorption, resonance Raman spectroscopy and electrochemical methods. This combination of methods in concert with quantum chemistry calculations allow detailed insights into the structural and electronic properties of electronic intermediates, which might be of functional importance in the overall solar-energy conversion achieved by the transition metal complexes investigated.In this study light induced excitation has been mimicked by electrochemical reduction and the intermediate redox state has been characterized spectroscopically. In particular we focus on systems baring an imidazole ligand coordinated to the Ru-ion, which � due to their unusually red-shifted absorption � present promising candidates for sensitizers in dye-sensitized solar cells. The spectroelectrochemical approach used deciphers the structure of the Ru complexes upon photoinduced charge accumulation.  Figure: Comparison of resonance Raman spectra of functional Ruthenium polypyridine complexes and its electrogenerated species evidence molecular structure changes of the intermediates formed upon reduction. Ligand reduction decrease the strength of binding, which is reflected in an energy down shift of vibrational frequencies  assigned to bipyridine modes. The work presented is supported by the Th�ringer Ministerium f�r Bildung, Wissenschaft und Kultur (grant no.: B514-09049 and grant no.: 2011 FE9096). Further financial support from the Fonds der chemischen Industrie (B. D.) is gratefully acknowledged. We acknowledge the COST Action CM 1202 Perspect-H2O.

Trapped in imidazole: How to accumulate multiple photoelectrons on a black absorbing ruthenium complex

247th National Meeting (2014)

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