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- W2479685736 abstract "The properties of a series of fixed-distance chlorophyll-porphyrin molecules are described. These molecules consist of a methyl pyrochlorophyllide a moiety that is directly bonded at its 2-position to the 5-position of a 2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-(ptolyl)porphyrin. Steric hindrance between adjacent substituents rigidly positions the Π systems of both macrocycles perpendicular to each other. The macrocycles were selectively metalated with zinc to give the four possible derivatives, HCHP, ZCHP, HCZP, and ZCZP (where H, Z, C, and P denote free base, Zn derivative, chlorin, and porphyrin, respectively). The lowest excited singlet states of HCHP and ZCHP, which are localized on HC and ZC, respectively, exhibit lifetimes and fluorescence quantum yields that are solvent-polarity-independent and do not differ significantly from those of chlorophyll itself. ZCZP and HCZP, however, display solvent-polarity-dependent photophysics. HCZP forms an ion-pair state following excitation in polar media, although ZCZP does not. Nevertheless, nonradiative decay is substantially enhanced in ZCZP as the solvent polarity increases. These effects are discussed in terms of mixing low-lying charge-transfer states of ZCZP into its locally excited singlet state. Enhanced nonradiative decay of excited heterodimers within bacterial reaction centers has recently been observed." @default.
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- W2479685736 date "1991-05-05" @default.
- W2479685736 modified "2023-09-27" @default.
- W2479685736 title "Solvent-Dependent Photophysics of Fixed-Distance Chlorophyll—Porphyrin Molecules" @default.
- W2479685736 doi "https://doi.org/10.1021/ba-1991-0228.ch008" @default.
- W2479685736 hasPublicationYear "1991" @default.
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