Rotational characterization of S F chalcogen bonds in the complex of 2,2,4,4-tetrafluoro-1,3-dithietane and difluoromethane

Sulfur chalcogen bonds (ChBs) play important roles in fields ranging from protein science to molecular self-assembly and organic conductor materials. Understanding of the intrinsic nature of sulfur ChBs is critical to reveal their functions. In this work, we report the first rotational spectroscopic...

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Bibliographic Details
Published inPhysical chemistry chemical physics : PCCP Vol. 21; no. 44; pp. 24659 - 24665
Main Authors Lu, Tao, Zheng, Yang, Gou, Qian, Hou, Gao-Lei, Feng, Gang
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 2019
Subjects
Chalcogen bonds
Charge distribution
Conductors
Energy of dissociation
Fourier transforms
Free energy
Heat of formation
Mathematical analysis
Organic chemistry
Quantum chemistry
Rotational spectra
Self-assembly
Spectrum analysis
Sulfur
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Summary:Sulfur chalcogen bonds (ChBs) play important roles in fields ranging from protein science to molecular self-assembly and organic conductor materials. Understanding of the intrinsic nature of sulfur ChBs is critical to reveal their functions. In this work, we report the first rotational spectroscopic investigation on the novel S F ChB in a 1 : 1 molecular complex of 2,2,4,4-tetrafluoro-1,3-dithietane (C 2 F 4 S 2 ) and difluoromethane (DFM). The rotational spectra measured with Fourier transform microwave spectroscopy on the six isotopologues of the complex allow the determination of the S F distance to be 2.9759(6) Å and the associated angle to be 157.90(3)°. Experimental results and quantum chemical calculations clearly support the formation of S F ChB in the complex. The uncovered structure also shows the existence of two C-H F and two C-F F-C contacts. Further theoretical analyses reveal the electrostatic and dispersion interactions to be dominant in stabilizing the complex, and the dissociation energy of the complex to be 15.2 kJ mol −1 . The nature of S F chalcogen bonds and C-H F and C-F F-C contacts was characterized by rotational spectroscopy for the first time.
Bibliography:Electronic supplementary information (ESI) available: The MP2/6-311++G(d,p) calculated equilibrium structures (Fig. S1); experimental transition frequencies of the six isotopologues of the complex (Tables S1-S3); experimental and theoretical coordinates of the three C and two S atoms (Table S4); stabilization energy analysis (Table S5); NPA charge distributions (Table S6). See DOI
10.1039/c9cp04628c
ISSN:1463-9076
1463-9084
DOI:10.1039/c9cp04628c