Dimerization of thianthrene radical cations as studied by in situESR and UV-Vis-NIRvoltammetry at different temperatures
文献情報
Philippe Hapiot, Lothar Dunsch
Electrochemically generated thianthrene radical cations (Th+˙) are shown to be reversibly transferred into dimers. The ratio of radical ion to dimer can be easily controlled by the thianthrene concentration and the temperature. Using temperature-dependent in situ UV-Vis spectroelectrochemistry the dimer formation was followed and superimposed optical spectra of the electrochemical reaction products were separated into those of the free radical and the dimer. Expanding the study to in situ ESR/UV-Vis-NIR spectroelectrochemical measurements at different temperatures the formation of the spinless dimer was proved and the extent of dimerized radical was determined quantitatively. Besides the sigma-dimer of thianthrene radical cation (Th+–Th+), the existence of a charge-transfer resonance structure (Th,Th)+˙ was detected in NIR spectra.
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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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