Determination of Hyperfine Coupling Constants of Fluorinated Diphenylacetylene Radical Anions by Magnetic Field-Affected Reaction Yield Spectroscopy

Victoria A Sannikova; Maria P Davydova; Peter S Sherin; Simon V Babenko; Valeri V Korolev; Alexander A Stepanov; Pavel V Nikul'shin; Evgeny V Kalneus; Sergei F Vasilevsky; Enrico Benassi; Anatoly R Melnikov

doi:10.1021/acs.jpca.8b10306

Determination of Hyperfine Coupling Constants of Fluorinated Diphenylacetylene Radical Anions by Magnetic Field-Affected Reaction Yield Spectroscopy

J Phys Chem A. 2019 Jan 17;123(2):505-516. doi: 10.1021/acs.jpca.8b10306. Epub 2019 Jan 3.

Authors

Victoria A Sannikova^{1

2}, Maria P Davydova^{1

3}, Peter S Sherin^{2

4}, Simon V Babenko¹, Valeri V Korolev¹, Alexander A Stepanov^{1

2}, Pavel V Nikul'shin⁵, Evgeny V Kalneus¹, Sergei F Vasilevsky^{1

2}, Enrico Benassi^{2

6}, Anatoly R Melnikov^{1

2}

Affiliations

¹ Institute of Chemical Kinetics and Combustion SB RAS , 3, Institutskaya Str. , 630090 Novosibirsk , Russian Federation.
² Novosibirsk State University , 2, Pirogova Str. , 630090 Novosibirsk , Russian Federation.
³ A.V. Nikolaev Institute of Inorganic Chemistry SB RAS , 3, Akademika Lavrentieva Ave. , 630090 Novosibirsk , Russian Federation.
⁴ International Tomography Center , 3a, Institutskaya Str. , 630090 Novosibirsk , Russian Federation.
⁵ N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS , 9, Akademika Lavrentieva Ave. , 630090 Novosibirsk , Russian Federation.
⁶ Department of Chemistry , Hexi University , 734000 Zhangye , China.

PMID: 30566354
DOI: 10.1021/acs.jpca.8b10306

Abstract

Magnetic field-affected reaction yield (MARY) spectroscopy is a spin chemistry technique for detecting short-lived radical ions. Having sensitivity to transient species with lifetimes as short as nanoseconds, MARY spectroscopy usually does not provide detailed information on their magnetic resonance parameters, except for simple systems with equivalent magnetic nuclei. In this work, the radical anions of two fluorinated diphenylacetylene derivatives with nonequivalent magnetic nuclei and unknown hyperfine coupling constants ( A_HF) were investigated by MARY spectroscopy. The MARY spectra were found to be resolved and have resonance lines in nonzero magnetic fields, which are determined by the A_HF values. Simple relationships between the positions of resonance MARY lines and the A_HF values were established from the analysis of the different Hamiltonian block contributions to the MARY spectrum. The obtained experimental A_HF values are in agreement with the results of quantum chemical calculations at the density functional theory level.