NDLI: A Supramolecular Tetrad Featuring Covalently Linked Ferrocene–Zinc Porphyrin–BODIPY Coordinated to Fullerene: A Charge Stabilizing, Photosynthetic Antenna–Reaction Center $Mimic^{†}$

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A Supramolecular Tetrad Featuring Covalently Linked Ferrocene–Zinc Porphyrin–BODIPY Coordinated to Fullerene: A Charge Stabilizing, Photosynthetic Antenna–Reaction Center $Mimic^{†}$

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Lim, Gary N. Zandler, Melvin E. D'souza, Francis Maligaspe, Eranda
Description	Author Affiliation: Lim GN ( Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX 76203-5017 (USA).)
Abstract	A novel photosynthetic-antenna–reaction-center model compound, comprised of $BF_{2}-chelated$ dipyrromethene (BODIPY) as an energy-harvesting antenna, zinc porphyrin (ZnP) as the primary electron donor, ferrocene (Fc) as a hole-shifting agent, and phenylimidazole-functionalized fulleropyrrolidine $(C_{60}Im)$ as an electron acceptor, has been synthesized and characterized. Optical absorption and emission, computational structure optimization, and cyclic voltammetry studies were systematically performed to establish the role of each entity in the multistep photochemical reactions. The energy-level diagram established from optical and redox data helped identifying different photochemical events. Selective excitation of BODIPY resulted in efficient singlet energy transfer to the ZnP entity. Ultrafast electron transfer from the $^{1}ZnP$ (formed either as a result of singlet–singlet energy transfer or direct excitation) or $^{1}C_{60}$ of the coordinated fullerene resulting into the formation of the $Fc–(C_{60}^{.−}Im:ZnP^{.+})–BODIPY$ radical ion pair was witnessed by femtosecond transient absorption studies. Subsequent hole migration to the ferrocene entity resulted in the $Fc^{+}–(C_{60}^{.+}Im:ZnP)–BODIPY$ radical ion pair that persisted for 7–15 μs, depending upon the solvent conditions and contributions from the triplet excited states of ZnP and $ImC_{60},$ as revealed by the nanosecond transient spectral studies. Better utilization of light energy in generating the long-lived charge-separated state with the help of the present “antenna–reaction-center” model system has been successfully demonstrated.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	51
Volume Number	20
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2014-12-15
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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