Journal of Physical Chemistry A, Vol.114, No.12, 4156-4162, 2010
Electron Transfer in the Supramolecular Donor-Acceptor Dyad of Zinc Hemiporphycene
In the present study, photoinduced electron transfer (ET) processes of supramolecular donor-acceptor dyads of Zn 2,3,7,8,11,12,17,18-octaethylhemiporphycene (ZnHPc) and axial ligands were investigated by using various spectroscopic methods. The formation of 1:1 dyads was confirmed by absorption spectral change during titration of axial ligand. The association constants were determined from the spectral change. Quenching of the fluorescence intensity was observed when electron acceptor ability of the axial ligand increased. The driving forces for ET were estimated based oil the estimated redox potentials and structural parameters. It became clear that various ZnHPc dyads showed FT because of slightly higher donor-ability and larger excitation energy of ZnHPc when compared to the corresponding dyads of Zn porphycene (ZnPcn). The transient absorption spectra during the sub-picosecond laser flash Photolysis showed the formation of charge separated state, that is, radical cation of ZnHPc and radical anion of axial ligand, from the singlet excited ZnHPc. The observed ET rates were compared with the previously reported values for Zn porphyrins and ZnPcn. The ET rates of ZnHPc were located between those observed with porphyrins and ZnPcn supramolecular dyads, even when the -Delta G values were similar to each other. This observation was explained oil the basis of the variation in reorganization energy and electronic coupling (V) values. Furthermore, distribution of HOMO electron density gave a plausible explanation for the variation in V values of these dyads.