Bio-inspired Photocatalytic Ruthenium Complexes: Synthesis, Optical Properties, and Solvatochromic Effect

Chemphyschem. 2018 Jan 19;19(2):220-226. doi: 10.1002/cphc.201701061. Epub 2017 Dec 29.

Abstract

We report the synthesis, characterization, and photo-physical properties of two new rutheniumII -phenol-imidazole complexes. These bio-mimetic complexes have potential as photocatalysts for water splitting. Owing to their multiple phenol-imidazole groups, they have a higher probability of light-induced radical formation than existing complexes. The newly synthesized complexes show improved overlap with the solar spectrum compared to other rutheniumII -phenol-imidazole complexes, and their measured lifetimes are suitable for light-induced radical formation. In addition, we conducted solvatochromic absorption measurements, which elegantly follow Marcus theory, and demonstrate the symmetry differences between the two complexes. The solvatochromic measurements further imply electron localization onto one of the ligands. The new complexes may find applications in photocatalysis, dye-sensitized solar cells, biomedicine, and sensing. Moreover, their multiple chelating units make them promising candidates for light-activated metal organic radical frameworks, i.e. metal-organic frameworks that contain organic radicals activated by light.

Keywords: Marcus theory; metal-organic frameworks; photocatalysis; solvatochromism; water splitting.