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Geometry- and solvent-polarity-dependent photoinduced electron transfer in conformationally restricted magnesium—free-base hybrid diporphyrins

✍ Scribed by Atsuhiro Osuka; Fumikazu Kobayashi; Kazuhiro Maruyama; Noboru Mataga; Tsuyoshi Asahi; Tadashi Okada; Iwao Yamazaki; Yoshinobu Nishimura


Book ID
103036509
Publisher
Elsevier Science
Year
1993
Tongue
English
Weight
445 KB
Volume
201
Category
Article
ISSN
0009-2614

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✦ Synopsis


Excited-state dynamics of a series of conformationally restricted magnesium-free-base hybrid diporphyrins (MgP-HsP) 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 ' (MgP)* to the HZP has been observed regardless of the spacer between the two subunits and the '(HsP)* thus formed decays with the same time constant with the reference monomeric H2P in each solvent. In DMF, the photoexcited state dynamics of MgP-HzP depends on the geometry of the models; charge separated state (MgP) +-(H,P)-is generated from both of the ' (MgP)* and I (H,P)* in hybrid diporphyrins with shorter separation, while only the singlet-singlet energy transfer from the '(MgP)* to the HsP has been observed for models with larger separations.