Geometry and solvent-polarity dependences of the relaxation dynamics of the singlet excited state of center-to-edge phosphorus(V) porphyrin heterodimers

The Journal of Physical Chemistry. B
Kenji NagaoHiroshi Segawa

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 ...Continue Reading

References

Oct 1, 1988·Proceedings of the National Academy of Sciences of the United States of America·C KirmaierD C Youvan
Dec 26, 2001·Chemical Reviews·A K BurrellD C Reid

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Citations

Jan 23, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Masaaki AbeYoshio Hisaeda
Jul 31, 2008·Inorganic Chemistry·Prashanth Kumar PoddutooriArt van der Est

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