- 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 novel photosynthetic-antenna-reaction-center model compound, comprised of BF2-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 (C60Im) 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 1ZnP (formed either as a result of singlet- singlet energy transfer or direct excitation) or 1C60 of the coordinated fullerene resulting into the formation of the Fc-(C60CIm:ZnPC+)-BODIPY radical ion pair was witnessed by femtosecond transient absorption studies. Subsequent hole migration to the ferrocene entity resulted in the Fc+-(C60C+Im:ZnP)-BODIPY radical ion pair that persisted for 7-15 ms, depending upon the solvent conditions and contributions from the triplet excited states of ZnP and ImC60, 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.
- Lim, Gary N.,Maligaspe, Eranda,Zandler, Melvin E.,D'Souza, Francis
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- Electronic energy harvesting multi BODIPY-zinc porphyrin dyads accommodating fullerene as photosynthetic composite of antenna-reaction center
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Efficient electronic energy transfer (EET) in the newly synthesized dyads comprised of zinc porphyrin covalently linked to one, two or four numbers of boron dipyrrin (BDP) entities is investigated. Both steady-state and time-resolved emission as well as t
- Maligaspe,Kumpulainen,Subbaiyan,Zandler,Lemmetyinen,Tkachenko,D'Souza
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p. 7434 - 7444
(2011/09/14)
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- Cyclic oligomers based on complementary Zn(ii) and Sn(iv)-porphyrins
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The aggregation of a 1: 1 mixture of complementary Sn(iv)- and Zn(ii)-porphyrins into cyclic decameric and dodecameric assemblies has been demonstrated by 1H NMR, GPC, DOSY and MALDI-TOF spectrometry.
- Metselaar, Gerald A.,Ballester, Pablo,De Mendoza, Javier
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experimental part
p. 777 - 783
(2009/06/19)
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- An efficient synthesis of tetraaryl porphyrins substituted with ester groups bearing long alkyl chains
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The synthesis of tetraaryl porphyrins substituted with long chain ester groups is described. The compounds are conveniently prepared from the methyl ester 1a via a base induced transesterification procedure. The method is also applicable for the synthesis of ester linked diporphyrins.
- Hombrecher,Ohm
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p. 2447 - 2456
(2007/10/02)
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