Distance-Dependent Electron Transfer Kinetics in Axially Connected Silicon Phthalocyanine-Fullerene Conjugates.

The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C60 dyads has been investigated. For this, two C60-SiPc-C60 dyads, 1 and 2, varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C60-SiPc-C60 1 where the SiPc and C60 are separated by a phenyl spacer, faster electron transfer was observed with kcs equal to 2.7×109 s-1 in benzonitrile. However, in the case of C60-SiPc-C60 2, where SiPc and C60 are separated by a biphenyl spacer, a slower electron transfer rate constant, kcs=9.1×108 s-1, was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3-20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc.+-C60 .- charge separated states (1.57 eV) populated the low-lying 3SiPc* (1.26 eV) prior returning to the ground state.