Caged Nitric Oxide–Thiyl Radical Pairs
- Zhuang Wu (1540450)
- Changyun Chen (6373019)
- Jie Liu (15128)
- Yan Lu (32611)
- Jian Xu (31545)
- Xiangyang Liu (102753)
- Ganglong Cui (1329708)
- Tarek Trabelsi (4524523)
- Joseph S. Francisco (1414543)
- Artur Mardyukov (1795174)
- André K. Eckhardt (5558144)
- Peter R. Schreiner (770003)
- Xiaoqing Zeng (1540453)
DOIAbstract
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
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