Intramolecular multiple Rehm–Weller plots in photoinduced electron transfer: competition between π- and n-type donor sites in benzylamines

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DOI 10.1039/A809968E

影响因子 3.676

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摘要

Earlier PET work has suggested that, for a given electron acceptor, distinct π- and n-type electron donors lead to distinct Rehm–Weller plots due to different Coulomb terms (C-terms) Cπ and Cn, respectively. We studied benzylamine donors which embody both types of donor site. The results support the key role of the C-term in determining electron transfer efficiencies. A thorough evaluation of the adiabatic ionization potential (IPa) of the π- and the n-moiety, serving as a measure of the corresponding relative oxidation potential (Eox), was crucial to arrive at these findings. Hence, for an electron donor embodying more than one donor site the observable PET rate constant is not necessarily related to the easiest oxidizable site, i.e. to Eox. This does not apply to photoinduced charge shift as here the C-term does not contribute to the driving force. Earlier useful correlations between Eox and IPa for π- and n-donors were updated.

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来源期刊

Physical Chemistry Chemical Physics

CiteScore: 5.5

自引率: 10.3%

年发文量: 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.