Synthesis and Characterization of a Series of Bis-homoleptic Cycloruthenates with Terdentate Ligands as a Family of Panchromatic Dyes

A series of six homoleptic bis-cyclometalated ruthenium complexes, Ru((NNC)-N-boolean AND-C-boolean AND)(2), is reported where (NNC)-N-boolean AND-C-boolean AND is a 6-(2,4-difluoro-3-R-3-phenyl)-4-R-2-4'-R-1-2,2'-bipyridine with R-3 = -H or -CF3 and R-2 and R-1 = -COOEt or -CF3. An effective synthesis of the ligands and the complexes is described. The UV-visible absorption studies demonstrate that these complexes are panchromatic dyes absorbing up to 900 nm. Importantly, the onset of absorption depends only on the substitution on the metalated phenyl, whereas the intensity of absorption throughout the spectra is a function of substituents on both the phenyl and the bipyridine moieties. The same trend is observed in electrochemistry as the redox gap depends only on the substitution on the metalated phenyl, whereas the oxidation and reduction potentials are a function of substituents on both the phenyl and the bipyridine moieties. Preliminary tests as sensitizer for dye-sensitized solar cells demonstrate that the number of anchoring groups on the dye has a major influence on the device efficiency.