Spectroscopic identification of the •SSNO isomers

Lina Wang; Zhuang Wu; Bo Lu; André K Eckhardt; Peter R Schreiner; Tarek Trabelsi; Joseph S Francisco; Qian Yao; Changjian Xie; Hua Guo; Xiaoqing Zeng

doi:10.1063/5.0020669

Spectroscopic identification of the •SSNO isomers

J Chem Phys. 2020 Sep 7;153(9):094303. doi: 10.1063/5.0020669.

Authors

Lina Wang¹, Zhuang Wu¹, Bo Lu², André K Eckhardt³, Peter R Schreiner³, Tarek Trabelsi⁴, Joseph S Francisco⁴, Qian Yao⁵, Changjian Xie⁶, Hua Guo⁵, Xiaoqing Zeng¹

Affiliations

¹ Department of Chemistry, Fudan University, Shanghai 200433, China.
² College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
³ Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, Giessen 35392, Germany.
⁴ Department of Earth and Environment Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6243, USA.
⁵ Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
⁶ Institute of Modern Physics, Shaanxi Key Laboratory for Theoretical Physics Frontiers, Northwest University, Xian, Shaanxi 710127, China.

PMID: 32891090
DOI: 10.1063/5.0020669

Abstract

Elusive [S, S, N, O] isomers including the perthiyl radical •SSNO are S/N hybrid species in the complex bioinorganic chemistry of signaling molecules H₂S and •NO. By mixing thermally generated disulfur (S₂) with •NO in the gas phase, •SSNO was generated and subsequently isolated in cryogenic Ar- and N₂-matrices at 10.0 K and 15.0 K, respectively. Upon irradiation with a 266 nm laser, •SSNO isomerizes to novel sulfinyl radicals cis-NSSO• and trans-NSSO• as well as thiyl radicals cis-OSNS• and trans-OSNS•, which have been characterized by combining matrix-isolation IR (¹⁵N-labeling) and UV/Vis spectroscopy and quantum chemical calculations at the CCSD(T)-F12/cc-pVTZ-F12 level of theory. The photo-induced reversible interconversion between NSSO• and OSNS• has also been observed.