title: Geometry and solvent-polarity dependences of the relaxation dynamics of the singlet excited state of center-to-edge phosphorus(V) porphyrin heterodimers.
abstract: Para- and meta-isomers of center-to-edge phosphorus(V) porphyrin heterodimers (p- and m-Pm-PCl2) composed of a phosphorus(V) tetraphenylporphyrin (P) and a phosphorus(V) tetrakis(4-methoxyphenyl)porphyrin (Pm) were synthesized to investigate the geometry and solvent-polarity dependences of the relaxation dynamics of the lowest singlet excited state (S1) of the porphyrin dimer. The geometrical difference between m- and p-Pm-PCl2 in solution was confirmed by 1H NMR on the basis of the porphyrin ring current model. By the photoexcitation of the dimers, only the fluorescence from 1Pm*-P was observed in both dimers because of the efficient singlet energy transfer from the higher energy 1P* to the lower energy 1Pm*. However, the 1Pm*-P fluorescence had features that differ from the typical fluorescence from monomeric 1Pm*, especially for the solvent-polarity dependence of the quantum yields. Furthermore, all the fluorescence decay curves of 1Pm*-P were double-exponential. The special fluorescence features of 1Pm*-P are due to the equilibrium between 1Pm*-P and the charge-transfer (CT) excited state of the dimer ((Pm-P)CT). By the excited-state equilibrium, 1Pm*-P is efficiently quenched through (Pm-P)CT in highly polar solvents. The contribution of (Pm-P)CT to the decay process of 1Pm*-P is more remarkable in m-Pm-PCl2 than in p-Pm-PCl2, depending on the interaction between the two porphyrin -systems in the heterodimer.
authors.affiliation: Department of Chemistry, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan.
authors.forename: Kenji
authors.initials: K
authors.lastname: Nagao
authors.forename: Yasuko
authors.initials: Y
authors.lastname: Takeuchi
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Segawa