Photoinduced electron transfer in a symmetrical diporphyrin–fullerene triad

Literature Information

Publication Date 2004-11-03
DOI 10.1039/B412326C
Impact Factor 3.676
Authors

Paul A. Liddell, Gerdenis Kodis, Darius Kuciauskas, Joakim Andréasson, Ana L. Moore, Thomas A. Moore, Devens Gust


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Abstract

Two triad molecules consisting of either two zinc, or two free-base porphyrins symmetrically joined to a fullerene via phenyleneethynylene-containing linkages have been synthesized, and their photochemistry investigated. In the zinc form of the triad, PZn–C60–PZn, excitation of a zinc porphyrin in 2-methyltetrahydrofuran solution is followed by photoinduced electron transfer to the fullerene with a time constant of 20 ps. The resulting PZn˙+–C60˙−–PZn charge-separated state is formed with a quantum yield of 98% and has a lifetime of 820 ps. The first excited singlet state of the free-base analog gives the P2H˙+–C60˙−–P2H charge-separated state with a time constant of 200 ps and a yield of 98%. The charge-separated state decays with a lifetime of 2.8 ns. The difference in the rates of photoinduced electron transfer is consistent with reaction in the normal region of the Marcus–Hush relationship of transfer rate and driving force, and charge recombination is consistent with Marcus–Hush inverted behavior. The presence of the two porphyrin electron donors in these triads enhances the absorption cross section for light collection, and the molecular framework employed could be used to prepare molecules with enhanced energy conversion or optoelectronic properties.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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