Porphyrin boxes constructed by homochiral self-sorting assembly: Optical separation, exciton coupling, and efficient excitation energy migration

meso-Pyridine-appended zinc(II) porphyrins Mn and their meso-mesolinked dimers Dn assemble spontaneously, in noncoordinating solvents such as CHCl ₃, into tetrameric porphyrin squares Sn and porphyrin boxes Bn, respectively. Interestingly, formation of Bn from Dn proceeds via homochiral self-sorting assembly, which has been verified by optical separations of B1 and B2. Optically pure enantiomers of B1 and B2 display strong Cotton effects in the CD spectra, which reflect the length of the pyridyl arm, thus providing evidence for the exciton coupling between the noncovalent neighboring porphyrin rings. Excitation energy migration processes within Bn have been investigated by steady-state and time-resolved spectroscopic methods in conjunction with polarization anisotropy measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly associated with the excitation energy migration process within the Bn boxes, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Förster-type incoherent energy hopping model by assuming a number of hopping sites of N = 4 and an exciton coherence length of L = 2. Consequently, the excitation energy hopping rates between the zinc(II) diporphyrin units have been estimated for B1 (48 ps)^-1, B2 (98 ± 3 ps)^-1, and B3 (361 ± 6 ps)^-1. Overall, the self-assembled porphyrin boxes Bn serve as a well-defined three-dimensional model for the light-harvesting complex.