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The potential of dimethylsilylene and isopropylidene U-spacers as bridges for photoinduced charge transfer (CT) in 4-cyano-4'-(dimethylamino)- and 4-cyano-4'-methoxy-substituted diphenyldimethylsilanes and 2,2-diphen- ylpropanes was studied. Fluorescence solvatochromism and time-resolved microwave conductivity measurements show that upon photoexcitation a charge separated state (D ¥+ UA ¥- )* is populated in all compounds. Excited state dipole moments for a given donor-acceptor combination are, irrespective of the bridge, equal. The CT states of the silanes are however lying at lower energies, implying that the presence of silicon thermodynamically facilitates the CT process. Cyclic voltammetry data of model compounds show that this is a consequence of the lowering of the acceptor reduction potential by the silicon bridge. It was however inferred from radiative decay rates that the electronic coupling between the CT and locally excited states as well as the coupling between the ground and CT state is larger for the carbon-bridged compounds. As shown by both solution and solid state electronic spectra and radiative decay rates, the photophysics of the DUA compounds are dominated by intensity borrowing of the CT transitions from transitions localized in the DU and UA chromophores.

Comparison between SiMe2 and CMe2 Spacers as σ-Bridges for Photoinduced Charge Transfer

Comparison between SiMe₂ and CMe₂ Spacers as σ-Bridges for Photoinduced Charge Transfer