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Intramolecular interaction of synthetic chlorophyll heterodyads with different π-skeletons

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Abstract

Two heterodyads were prepared from the chemical modification of naturally occurring (bacterio)chloro-phyll-a and composed of a chlorin π-skeleton linked to a porphyrin or bacteriochlorin π-system. Zinc methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, was covalently linked with its 17, 18-didehydrogenated species (zinc methyl pyroprotopheophorbide-a) or its trans-7, 8-dihydrogenated analog (zinc methyl pyrobacteriopheophorbide-a as one of the bacteriochlorophyll-a derivatives) through ethylene glycol diester at their 17-propionate residues. In benzene, the central zinc atoms of the synthetic conjugates were coordinated by two methanol molecules which were hydrogen-bonded with the 13-keto-carbonyl groups in a dyad molecule. The methanol locked, y-axis aligned, and slipped cofacial conformers showed two apparent Qy bands at longer wavelengths than those of the composite zinc complex monomers. The red-shifted Qy bands are ascribable to the exciton coupling of the two different π-systems in the folded heterodyad conformers. The synthetic heterodyads could be models of chloro-phyll-a/c dimers in the light-harvesting antennas of chromophytes including fucoxanthin–chlorophyll proteins in diatoms and also chlorophyll-a species interacting with bacteriochlorophyll-a or g species in the charge-separating reaction centers of green sulfur bacteria or heliobacteria, respectively.

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Authors and Affiliations

  1. Graduate School of Life Sciences, Ritsumeikan University, 525-8577, Kusatsu, Shiga, Japan

    Hitoshi Tamiaki, Kazuhiro Fukai & Soichi Nakamura

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  1. Hitoshi Tamiaki
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  2. Kazuhiro Fukai
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  3. Soichi Nakamura
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Correspondence to Hitoshi Tamiaki.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/ c9pp00373h

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Tamiaki, H., Fukai, K. & Nakamura, S. Intramolecular interaction of synthetic chlorophyll heterodyads with different π-skeletons. Photochem Photobiol Sci 19, 332–340 (2020). https://doi.org/10.1039/c9pp00373h

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  • DOI: https://doi.org/10.1039/c9pp00373h

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