Aggregation-induced increase of the quantum yield of electron injection from chalcogenorhodamine dyes to TiO₂

We used transient absorption spectroscopy to characterize excited-state electron injection from a 2,7-bis(dimethylamino)-9-(2-thienyl-5-carboxy) selenoxanthylium dye (1-Se) and a 2,7-bis(dimethylamino)-9-(3-thienyl-2-carboxy) selenoxanthylium dye (2-Se) to TiO₂. Monolayers of 1-Se on nanocrystalline TiO₂ films consisted of both H-aggregated and nonaggregated dyes, whereas 2-Se underwent little or no aggregation upon adsorption. Two transient spectral signals were correlated with the dication radicals (1-Se⁺ and 2-Se⁺) generated by electron injection: an absorption at wavelengths shorter than 540 nm and a bleach from approximately 540-650 nm. Relative quantum yields for electron injection (φ_inj) were calculated from the measured amplitudes of these signals. The value of φ_inj for H-aggregated 1-Se was approximately 2-fold greater than φ_inj for nonaggregated 1-Se and approximately 3-fold greater than φ_inj for nonaggregated 2-Se. Thus, H-aggregation can increase both the light-harvesting efficiencies and the electron-injection yields of rhodamine derivatives. Our findings suggest that controlled aggregation of organic dyes may represent an attractive strategy for improving the global energy-conversion efficiencies of organic dye-sensitized solar cells and photocatalysts.