C···S Tetrel Bond Favored in the Phenyl Isothiocyanate-CO2 Complex: A Rotational Study

Siyu Zou; Juncheng Lei; Tianyue Gao; Xuefang Xu; Qian Gou

doi:10.1021/acs.jpca.3c05187

C···S Tetrel Bond Favored in the Phenyl Isothiocyanate-CO₂ Complex: A Rotational Study

J Phys Chem A. 2023 Nov 30;127(47):9959-9965. doi: 10.1021/acs.jpca.3c05187. Epub 2023 Nov 18.

Authors

Siyu Zou¹, Juncheng Lei¹, Tianyue Gao¹, Xuefang Xu^{1

2}, Qian Gou^{1

2}

Affiliations

¹ Department of Chemistry, School of Chemistry and Chemical Engineering, Chongqing University, Daxuecheng South Rd. 55, 401331 Chongqing, China.
² School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Daxuecheng South Rd. 55, 401331 Chongqing, China.

PMID: 37979188
DOI: 10.1021/acs.jpca.3c05187

Abstract

The rotational spectrum of the phenyl isothiocyanate-CO₂ complex was investigated by pulsed-jet Fourier transform microwave spectroscopy complemented by quantum chemical calculations. Only one isomer, with CO₂ almost in the plane of phenyl isothiocyanate, has been detected in the pulsed jet, of which the spectrum displays a quadrupole coupling hyperfine structure due to the presence of a ¹⁴N nucleus (I = 1). This structure is nearly equal to the lowest energy geometry obtained by B3LYP-D3(BJ)/6-311++G(d,p), which has been dominated by a C···S tetrel bond (n → π* interaction) and one secondary C-H···O hydrogen bond (n → σ* interaction). Molecular electrostatic potential and natural bond orbital analysis were used to characterize the noncovalent interactions of the complex. The results from this study would lay the groundwork for the design and advancement of materials that exhibit high efficiency in capturing CO₂.