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• W2000617650 abstract "A project to investigate the parameters that determine the efficiency of biomimetic porphyrin quinone model compounds for photosynthesis is described. It should aid in understanding the origin of the high efficiency of energy conversion in the light-induced charge separation in photosynthesis. Specifically, the contribution of the electronic matrix element to the electron transfer (ET) rates is addressed. Targeting the electronic structure of the ET components, EPR (electron paramagnetic resonance) and ENDOR (electron nuclear double resonance) spectroscopy were performed on the appropriate radical derivatives of the porphyrins and quinones to determine MO coefficients. Together with semiempirical MO methods, these coefficients were used to obtain information on the frontier orbitals of the donor and acceptor moieties, the porphyrins, and quinones of the model compounds. The porphyrin frontier orbitals (HOMO and LUMO) have been implicated in the balance of ET rates for charge separation and charge recombination, which is related to the efficiency. A model is presented to correlate the substitution pattern of the porphyrin with the efficiency of the model compound. In particular, the effect of porphyrin substitution, including the covalent link to an acceptor, and the comparison of porphyrins with chlorins and chlorophylls are addressed. The model allows for a quantification of these effects in some cases. Differences in the frontier orbital structure suggest that the [5,10,15,20 tetraaryl(alkyl)porphyrinato]metal complexes are sufficiently different from chlorophylls to be nonideal model compounds. These results are related to recent publications, and possible improvements of experimental and theory approaches are addressed." @default.
• W2000617650 created "2016-06-24" @default.
• W2000617650 creator A5078253107 @default.
• W2000617650 date "2001-12-01" @default.
• W2000617650 modified "2023-09-26" @default.
• W2000617650 title "The Role of the Electronic Structure of the Porphyrin as Viewed by EPR/ENDOR Methods in the Efficiency of Biomimetic Model Compounds for Photosynthesis" @default.
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• W2000617650 doi "https://doi.org/10.1002/1099-0690(200112)2001:23<4379::aid-ejoc4379>3.0.co;2-6" @default.
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