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Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion.

ABSTRACT: The rapidly growing interest in photocatalytic systems for direct solar fuel production such as hydrogen generation from water splitting is grounded in the unique opportunity to achieve charge separation in molecular systems provided by electron transfer processes. In general, both photoinduced and catalytic processes involve complicated dynamics that depend on both structural and electronic effects. Here the excited state landscape of metal centered light harvester-catalyst pairs is explored using density functional theory calculations. In weakly bound systems, the interplay between structural and electronic factors involved can be constructed from the various mononuclear relaxed excited states. For this study, supramolecular states of electron transfer and excitation energy transfer character have been constructed from constituent full optimizations of multiple charge/spin states for a set of three Ru-based light harvesters and nine transition metal catalysts (based on Ru, Rh, Re, Pd, and Co) in terms of energy, structure, and electronic properties. The complete set of combined charge-spin states for each donor-acceptor system provides information about the competition of excited state energy transfer states with the catalytically active electron transfer states, enabling the identification of the most promising candidates for photocatalytic applications from this perspective.

SUBMITTER: Fredin LA

PROVIDER: S-EPMC5181788 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion.

Fredin Lisa A LA Persson Petter P

The Journal of chemical physics 20160901 10

The rapidly growing interest in photocatalytic systems for direct solar fuel production such as hydrogen generation from water splitting is grounded in the unique opportunity to achieve charge separation in molecular systems provided by electron transfer processes. In general, both photoinduced and catalytic processes involve complicated dynamics that depend on both structural and electronic effects. Here the excited state landscape of metal centered light harvester-catalyst pairs is explored us ...[more]

PMID: 27634263

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Project description:A new set of [Cu(phen)2]+ based rotaxanes, featuring [60]-fullerene as an electron acceptor and a variety of electron donating moieties, namely zinc porphyrin (ZnP), zinc phthalocyanine (ZnPc) and ferrocene (Fc), has been synthesized and fully characterized with respect to electrochemical and photophysical properties. The assembly of the rotaxanes has been achieved using a slight variation of our previously reported synthetic strategy that combines the Cu(i)-catalyzed azide-alkyne cycloaddition reaction (the "click" or CuAAC reaction) with Sauvage's metal-template protocol. To underline our results, complementary model rotaxanes and catenanes have been prepared using the same strategy and their electrochemistry and photo-induced processes have been investigated. Insights into excited state interactions have been afforded from steady state and time resolved emission spectroscopy as well as transient absorption spectroscopy. It has been found that photo-excitation of the present rotaxanes triggers a cascade of multi-step energy and electron transfer events that ultimately leads to remarkably long-lived charge separated states featuring one-electron reduced C60 radical anion (C60?-) and either one-electron oxidized porphyrin (ZnP?+) or one-electron oxidized ferrocene (Fc?+) with lifetimes up to 61 microseconds. In addition, shorter-lived charge separated states involving one-electron oxidized copper complexes ([Cu(phen)2]2+ (? < 100 ns)), one-electron oxidized zinc phthalocyanine (ZnPc?+; ? = 380-560 ns), or ZnP?+ (? = 2.3-8.4 ?s), and C60?- have been identified as intermediates during the sequence. Detailed energy diagrams illustrate the sequence and rate constants of the photophysical events occurring with the mechanically-linked chromophores. This work pioneers the exploration of mechanically-linked systems as platforms to position three distinct chromophores, which are able to absorb light over a very wide range of the visible region, triggering a cascade of short-range energy and electron transfer processes to afford long-lived charge separated states.

Dataset Information

Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion.

Publications

Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion.

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