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The state properties of the exciton formed by the rapid photodimerization of the axial Zn-porphyrin ligand in a porphyrin dyad are determined by measuring time-resolved fluorescence spectra. The kinetics of the fluorescence decay of the oligomer, which results from the rapid (∼70 ns) formation of the exciton from two Zn-porphyrin ligands in a dimeric axial-ligand pair, are investigated in a new mixed-sandwich porphyrin dyad containing both a macrocycle-to-ligand and a C-H···π interaction. The mixing of the populations of the two states, i.e., the Zn-porphyrin exciton and the Zn-porphyrin radical cation, are identified from the two major decay pathways observed in the fluorescence decay: (1) a fast decay pathway involving mainly the Zn-porphyrin radical cation (T1e = 1.9 ns) and (2) a slower decay pathway involving mainly the Zn-porphyrin exciton (T1a = 11.3 ns). The difference in T1a/T1e ratios, 0.40, indicates that the C-H···π interaction is a factor that competes with the ligand-to-macrocycle transfer in the formation of the exciton. The results suggest that the decrease in the lifetime of the exciton, T1a, is due to the mixed population of the excited states, which are caused by the strong interactions between the macrocycle and the ligand. The strong competition between two transfer paths is related to the fact that the exciton consists of four electrons localized at the metal centers (two at the axial and two at the equatorial sites) and the on-site π-conjugation of the macrocycle. The macrocycle-to-ligand transfer is influenced by the ligand lability, whereas the C-H···π interaction is related to the geometry of the ligand.Australia has been embroiled in a bitter debate about its policy towards asylum-seekers arriving
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