Visible light‐induced photodeoxygenation of polycyclic selenophene Se‐oxides. (22nd September 2020)

• Record Type: Journal Article
• Authors: Chintala, Satyanarayana M.; Throgmorton, John C.; Maness, Peter F.; McCulla, Ryan D.
• Is Part Of: Journal of physical organic chemistry. Volume 34:Number 3(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-09-22
• Subjects: photooxidation -- photodeoxygenation -- selenoxide; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.4144
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract: Photodeoxygenation of dibenzothiophene S ‐oxide (DBTO) is believed to produce ground‐state atomic oxygen [O( 3 P)] in solution. Compared with other reactive oxygen species (ROS), O( 3 P) is a unique oxidant as it is potent and selective. Derivatives of DBTO have been used as O( 3 P)‐precursors to oxidize variety of molecules, including plasmid DNA, proteins, lipids, thiols, and other small organic molecules. Unfortunately, the photodeoxygenation of DBTO requires ultraviolet irradiation, which is not an ideal wavelength range for biological systems, and has a low quantum yield of approximately 0.003. In this work, benzo[ b ]naphtho[1, 2‐ d ]selenophene Se ‐oxide, benzo[ b ]naphtho[2, 1‐ d ]selenophene Se ‐oxide, dinaphtho[2, 3‐ b :2', 3'‐ d ]selenophene Se ‐oxide, and perylo[1, 12‐ b, c, d ]selenophene Se ‐oxide were synthesized, and their ability to utilize visible light for generating O( 3 P) was interrogated. Benzo[ b ]naphtho[1, 2‐ d ]selenophene Se ‐oxide produces O( 3 P) upon irradiation centered at 420 nm. Additionally, benzo[ b ]naphtho[1, 2‐ d ]selenophene Se ‐oxide, benzo[ b ]naphtho[2, 1‐ d ]selenophene Se ‐oxide, and dinaphtho[2, 3‐ b :2', 3'‐ d ]selenophene Se ‐oxide produce O( 3 P) when irradiated with UVA light and have quantum yields of photodeoxygenation ranging from 0.009 to 0.33. This work increases the utility of photodeoxygenation by extending the range of wavelengths that can be used to generate O( 3 P) in solution. Abstract : Polycyclic selenoxides were synthesized, and their ability to generate O( 3 P) by irradiation of both UVA and visible light was investigated. The quantum yields of photodeoxygenation of these selenoxides are higher than dibenzothiophene S ‐oxide, a commonly used O( 3 P)‐precursor. Additionally, benzo[ b ]naphtho[1, 2‐ d ]selenophene Se ‐oxide produced O( 3 P) upon irradiation using bulbs centered at 420 nm.