Conformational Gating of Charge Separation in Porphyrin Oligomer-Fullerene Systems

The rate of the photoinduced charge-separation in C60-terminated butadiyne-linked porphyrin oligomers Pn (n = 4, 6) is strongly influenced by their molecular conformation. In these systems, the presence of the butadiyne linkers gives rise to a broad distribution of conformations in the ground state, due to an almost barrierless rotation of individual porphyrin units in the oligomer chain. The conformational states of these oligomers, either twisted or planar, could be selected by varying the excitation wavelength, thereby providing different initial excited states for charge separation. Charge separation in the different conformers was followed using both steady-state and 2D time-resolved emission using a streak camera system. Singular value decomposition (SVD) analysis applied on streak camera data provides here a powerful tool to study the conformational dependence of the charge separation in long PnC60 systems. Both the kinetics and spectral changes accompanying charge separation could be analyzed for different populations of conformation. From this analysis we show that, for both systems studied, twisted conformations undergo faster charge separation than planar conformations. This disparity in charge separation rates was ascribed mainly to the difference in driving force for charge separation between twisted and planar conformations. Charge separation was also studied in oligomers P nC60 coordinated to an octadentate ligand T8 that hinders the rotation of porphyrin subunits. The semicircular complexes P nC60-T8 show dramatic changes in their spectral properties, as well as slow excitation wavelength independent rate of charge separation and corresponding low efficiency compared to their linear counterparts. This slow charge separation rate was attributed to fast relaxation to the lowest excited vibronic state and lack of driving force for charge separation in these close to planar semicircular systems; i.e., the template systems behave like "normal" donor-acceptor systems without slow conformational relaxation. This work illustrates how control of conformation can be used to tune the rate of charge separation. © 2013 American Chemical Society