曾小庆教授与北京师范大学崔刚龙教授、宾夕法尼亚大学Joseph S. Francisco教授合作在 J. Am. Chem. Soc. 上发表研究论文

Caged Nitric Oxide–Thiyl Radical Pairs

Zhuang WuChangyun ChenJie LiuYan LuJian XuXiangyang LiuGanglong Cui*崔刚龙Tarek Trabelsi§Joseph S. Francisco*§Artur Mardyukov#André K. Eckhardt#Peter R. Schreiner#, and Xiaoqing Zeng*(曾小庆)

  

College of Chemistry, Chemical Engineering and Materials ScienceSoochow University, Suzhou 215123, China

Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of ChemistryBeijing Normal University, Beijing 100875, China

§Department of Earth and Environmental Science and Department of ChemistryUniversity of Pennsylvania, Philadelphia, Pennsylvania 19104, United States

#Institute of Organic ChemistryJustus Liebig UniversityHeinrich-Buff-Ring 17, 35392 Giessen, Germany

Z.W. and C.Y.C. contributed equally to this work.

  

J. Am. Chem. Soc.2019141 (8), 3361--3365

  

S-Nitrosothiols (RSNO) are exogenous and endogenous sources of nitric oxide in biological systems due to facile homolytic cleavage of the S–N bonds. By following the photolytic decomposition of prototypical RSNO (R = Me and Et) in Ne, Ar, and N2 matrixes (<10 K), elusive caged radical pairs consisting of nitric oxide (NO•) and thiyl radicals (RS•), bridged by O···S and H···N connections, were identified with IR and UV/vis spectroscopy. Upon red-light irradiation, both caged radical pairs (RS•···•ON) vanish and reform RSNO. According to the calculation at the CASPT2(10,8)/cc-pVDZ level (298.15 K), the dissociation energy of MeS•···•ON amounts to 4.7 kcal mol–1.

  

  

链接:https://pubs.acs.org.ccindex.cn/doi/10.1021/jacs.8b12746