TY - JOUR

T1 - Photochemistry of cerium(IV) ammonium nitrate (CAN) in acetonitrile

AU - Glebov, Evgeni M.

AU - Grivin, Vjacheslav P.

AU - Plyusnin, Victor F.

AU - Fedunov, Roman G.

AU - Pozdnyakov, Ivan P.

AU - Yanshole, Vadim V.

AU - Vasilchenko, Danila B.

N1 - Funding Information: The financial support of the Russian Foundation of Basic Research (Grant № 20-03-00708_a) is gratefully acknowledged. VY thanks Ministry of Science and Higher Education of the Russian Federation for the access to MS equipment. Publisher Copyright: © 2021 Elsevier B.V.

PY - 2021/9/1

Y1 - 2021/9/1

N2 - Cerium ammonium nitrate (NH4)2CeIV(NO3)6 (CAN) is widely used as a photolytic source of NO3[rad] radicals in acetonitrile. In spite of that, the mechanistic aspects of CAN photochemistry were poorly discussed in the literature. In this work CAN photochemistry in CH3CN was studied using the combination of stationary methods and laser flash photolysis. In accordance with the literature, the inner-sphere electron transfer was found to be the primary photochemical process. The (NH4)2CeIII(NO3)5(CH3CN) complex was found to be the only reaction product formed with the rather high quantum yield (0.6 and 0.4 upon 308 and 355 nm excitation correspondingly). The NO3[rad] radicals decay is mainly caused by the second-order reactions; their rate constants are determined. In addition to the direct release of the NO3[rad] radicals, a part of the light-excited CAN molecules were found to form the radical complex [(NH4)2CeIII(NO3)5…NO3[rad]], which lifetime is ca. 2 μs.

AB - Cerium ammonium nitrate (NH4)2CeIV(NO3)6 (CAN) is widely used as a photolytic source of NO3[rad] radicals in acetonitrile. In spite of that, the mechanistic aspects of CAN photochemistry were poorly discussed in the literature. In this work CAN photochemistry in CH3CN was studied using the combination of stationary methods and laser flash photolysis. In accordance with the literature, the inner-sphere electron transfer was found to be the primary photochemical process. The (NH4)2CeIII(NO3)5(CH3CN) complex was found to be the only reaction product formed with the rather high quantum yield (0.6 and 0.4 upon 308 and 355 nm excitation correspondingly). The NO3[rad] radicals decay is mainly caused by the second-order reactions; their rate constants are determined. In addition to the direct release of the NO3[rad] radicals, a part of the light-excited CAN molecules were found to form the radical complex [(NH4)2CeIII(NO3)5…NO3[rad]], which lifetime is ca. 2 μs.

KW - NO radical

KW - Acetonitrile

KW - Cerium ammonium nitrate (CAN)

KW - Laser flash photolysis

KW - Photochemistry

KW - Photoreduction

UR - http://www.scopus.com/inward/record.url?scp=85110392889&partnerID=8YFLogxK

U2 - 10.1016/j.jphotochem.2021.113440

DO - 10.1016/j.jphotochem.2021.113440

M3 - Article

AN - SCOPUS:85110392889

VL - 418

JO - Journal of Photochemistry and Photobiology A: Chemistry

JF - Journal of Photochemistry and Photobiology A: Chemistry

SN - 1010-6030

M1 - 113440

ER -