Abstract
Excited-state dynamics of a series of conformationally restricted magnesium—free-base hybrid diporphyrins (MgPH 2P) have been studied by fluorescence lifetime measurement and picosecond time-resolved transient absorption spectroscopy. Upon photoexcitation in toluene and THF, intramolecular singlet-singlet energy transfer from the 1(MgP)* to the H 2P has been observed regardless of the spacer between the two subunits and the 1(H 2P)* thus formed decays with the same time constant with the reference monomeric H 2P in each solvent. In DMF, the photoexcited state dynamics of MgPH 2P depends on the geometry of the models; charge separated state (MgP) +—(H 2P) − is generated from both of the 1(MgP)* and 1(H 2P)* in hybrid diporphyrins with shorter separation, while only the singlet—singlet energy transfer from the 1(MgP)* to the H 2P has been observed for models with larger separations.
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