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Self-assembled nanoscale photomimetic models: structure and related dynamics

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DOI
10.1016/s0301-0104(01)00516-x
Authors
Zenkevich, E. I.
Borczyskowski, C. von
Shulga, A. M.
Bachilo, S. M.
Rempel, U.
Willert, A.
Date
2002
Bibliographic entry
Self-assembled nanoscale photomimetic models: structure and related dynamics / E. I. Zenkevich [et al.] // Chemical Physics. – 2002. – Vol. 275, № 1-3. – P. 185-209.
Abstract
Using static and time-resolved measurements, dynamics of non-radiative relaxation processes have been studied in self-assembled porphyrin triads of various geometry, containing the main biomimetic components, Zn–porphyrin dimers, free-base extra-ligands (porphyrin, chlorin or tetrahydroporphyrin), and electron acceptors A (quinone or pyromellitimide). The strong quenching of the dimer fluorescence is due to energy and sequential electron transfer (ET) processes to the extra-ligand (~0.9–1.7 ps), which are faster than a slower ET (34–135 ps) from the dimer to covalently linked A in toluene at 293 K. The extra-ligand S₁-state decay (τₛ = 940–2670 ps) is governed by competing processes: a bridge (dimer) mediated long-range (r_DA = 18–24 Å) superexchange ET to an acceptor, and photoinduced hole transfer from the excited extra-ligand to the dimer followed by possible superexchange ET steps to low-lying charge transfer states of the triads. The subsequent ET steps dimer → monomer → A taking place in the triads, mimic the sequence of primary ET reactions in photosynthetic reaction centers in vivo. © 2002 Elsevier Science B.V. All rights reserved.
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https://rep.bntu.by/handle/data/30175
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