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Effects of Paramagnetic Lanthanide Ions On Decay Process of Photogenerated Radical Pairs in Porphyrin-Viologen Linked Compounds At Reversed Micellar Surfaces

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Radical pairs were generated in reversed micelles by laser excitation of zinc tetraphenylporphyrin-viologen linked compounds (ZPnV) with a polymethylene spacer (-(CH2)n-; n = 4, 6 and 8). The optical transient-absorption and chemically induced dynamic electron polarization (CIDEP) spectra indicated that paramagnetic lanthanide ions invariably accelerated the decay process of the radical pairs at 0.3 T. The typical E/A/E/A spectra for the ZP6V and ZP8V systems were explained as due to S-T0 mixing and electron-spin relaxation between Zeeman-splitted triplet sublevels. In the case of ZP4V, the paramagnetic Gd3+ ion accelerated the radical decay process even at zero-magnetic field, and strong emissive CIDEP spectra evolved with the elapsed time after laser excitation. Appreciable contribution of S-T level crossing in the radical decay process was suggested to account for the novel features of the ZP4V system.

Affiliations: 1: Department of Chemical Science and Technology, Faculty of Engineering Kyushu University, Hakozaki, Fukuoka 812, Japan


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