Benzene cation radical in mesoporous silicate: EPR detection of unusually stabilized Jahn–Teller distortion

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DOI 10.1039/A901061K
影响因子 3.676
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摘要

It has been found that the benzene cation radical (Bz+) is produced by radiolysis of a phenyl-substituted mesoporous silicate MCM-41 (Ph-MCM), and it shows a static Jahn–Teller distortion even at 77 K. The distorted structure deduced from the electron paramagnetic resonance (EPR) spectrum is almost equal to that reported for the cation radical observed in CFCl3 at 4.2 K, the singly occupied molecular orbital (SOMO) of which has been assigned to Ψs. On the other hand, Bz+ produced by radiolysis of benzene molecules adsorbed on Ph-MCM as well as on MCM-41 give dynamically averaged EPR spectra at 77 K, although the dynamics are frozen at 4.2 K. On radiolysis of "‘as-synthesized’' phenyl-MCM, not Bz+ but C6H5+–Si–R is generated. The trapping sites of Bz+ in the mesoporous silicates and the mechanism of stabilization of the distorted form are discussed.

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Physical Chemistry Chemical Physics

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.

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