Photochemical Hydroxyl Group Abstraction from N-Hydroxypyridine-2(1 H)-thione Isolated in a Solid Hydrogen Matrix: Photogeneration of 2-Mercaptopyridine

Molecules. 2024 Nov 20;29(22):5472. doi: 10.3390/molecules29225472.

Abstract

Monomers of N-hydroxypyridine-2(1H)-thione were isolated in low-temperature matrices of solid normal hydrogen (n-H2). The matrix-isolated compound was irradiated with UV-B (λ = 305 nm) or UV-A (λ > 360 nm) light. Upon such irradiation, the initial form of N-hydroxypyridine-2(1H)-thione was completely consumed and converted into photoproducts. 2-Mercaptopyridine and water were identified as the main products of these photochemical transformations. Identification of photoproduced 2-mercaptopyridine is unquestionable. It is based on the identity of two sets of IR bands: (i) the bands observed in the IR spectrum recorded (in a separate experiment) for monomers of 2-mercaptopyridine trapped in an n-H2 matrix and (ii) a set of IR bands observed in the spectrum recorded after UV irradiation of N-hydroxypyridine-2(1H)-thione. It should be emphasized that the UV-induced processes, occurring for N-hydroxypyridine-2(1H)-thione isolated in an n-H2 matrix, lead to products that are significantly different from those generated from the compound trapped in solid Ar or in solid N2.

Keywords: 2-mercaptopyridine-N-oxide; IR spectra; cage effect; hydroxyl radical; omadine; photochemistry; pyridylthiyl radical; pyrithione; reactive matrix.

Grants and funding

The authors acknowledge financial support from the Institute of Physics, Polish Academy of Sciences. The Chemical Engineering and Renewable Resources for Sustainability (CERES) research centre is supported by the Portuguese Science Foundation (“Fundação para a Ciência e a Tecnologia”, FCT) through FCT projects UIDB/EQU/00102/2020 (DOI: 10.54499/UIDB/00102/2020) base funding, UIDP/EQU/00102/2020 (DOI: 10.54499/UIDP/00102/2020) programmatic funding.