Novel Heteroleptic Ruthenium(II) Complexes with 2,2'- Bipyridines Containing a Series of Electron-Donor and Electron-Acceptor Substituents in 4,4'-Positions: Syntheses, Characterization, and Application as Sensitizers for ZnO Nanowire-Based Solar Cells.

A novel series of complexes of the formula Ru(4,4'-X-bpy)(Mebpy-CN) (X = -CH, -OCH, -N(CH); Mebpy-CN = 4-methyl-2,2'-bipyridine-4'-carbonitrile) have been synthesized and characterized by spectroscopic, electrochemical, and photophysical techniques. Inclusion of the electron-withdrawing substituent -CN at one bpy ligand and different electron-donor groups -X at the 4,4'-positions of the other two bpy ligands produce a fine tuning of physicochemical properties. Redox potentials, electronic absorption maxima, and emission maxima correlate well with Hammett's σ parameters of X. Quantum mechanical calculations are consistent with experimental data. All the complexes can be anchored through the nitrile moiety of Mebpy-CN over ZnO nanowires in dye-sensitized solar cells that exhibit an improvement of light to electrical energy conversion efficiency as the electronic asymmetry increases in the series.