Chalcogen bond and internal dynamics of the 2,2,4,4-tetrafluoro-1,3-dithietane⋯water complex

Literature Information

Publication Date 2019-06-25
DOI 10.1039/C9CP03301G
Impact Factor 3.676
Authors

Yan Jin, Xiaolong Li, Qian Gou, Gang Feng, Jens-Uwe Grabow, Walther Caminati


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Abstract

The rotational spectrum of the 2,2,4,4-tetrafluoro-1,3-dithietane⋯water complex has been investigated by high resolution rotational spectroscopy. Experimental evidence and quantum theoretical analyses revealed that the two moieties are linked together through a dominant S⋯O chalcogen bond. Two secondary F⋯O interactions contribute to the stability of the complex. The rotational transitions of four isotopologues are split into two component lines due to the internal rotation of the water moiety around its C2 axis. In the HDO isotopologue, a small μc dipole moment component is generated which inverts upon internal rotation of water, allowing the experimental determination of the tunneling splitting (21.46(5) GHz). Such splitting can be reproduced with a one-dimensional flexible model when the barrier to internal rotation of water is 87.4(2) cm−1.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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