Influence of Polarity and Ionic Strength on Intramolecular Spin Exchange in a Short Nitroxide Biradical, Containing Sulphur Atom in the Bridge | Sciact - CRIS-system of Boreskov Institute of Catalysis

Influence of Polarity and Ionic Strength on Intramolecular Spin Exchange in a Short Nitroxide Biradical, Containing Sulphur Atom in the Bridge Full article

Journal

Applied Magnetic Resonance
ISSN: 0937-9347 , E-ISSN: 1613-7507

Output data

Year: 2018, Volume: 49, Number: 10, Pages: 1059-1073 Pages count : 15 DOI: 10.1007/s00723-018-1041-y

Tags

ConformationsElectron spin resonance spectroscopyIon exchangeIonic liquidsParamagnetic resonanceQuantum chemistrySulfur

Authors

Kokorin A.I. ^1,2 , Mladenova-Kattnig B.Y. ³ , Gromov O.I. ⁴ , Shubin A.A. ^5,6 , Zaripov R.B. ⁷ , Grampp G. ³

Affiliations

1	N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation
2	Plekhanov Russian University of Economics, Moscow, Russian Federation
3	Institute of Physical and Theoretical Chemistry, Graz University of Technology, Graz, Austria
4	Chemistry Department, M. V. Lomonosov Moscow State University, Moscow, Russian Federation
5	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russian Federation
6	Novosibirsk State University, Novosibirsk, Russian Federation
7	Zavoisky Kazan Physical-Technical Institute, FRC Kazan Scientifc Center of RAS, Kazan, Russian Federation

A short nitroxide biradical: O=S(OR6)2 (BS), where OR6 is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, has been studied by electron paramagnetic resonance spectroscopy at X-, Q-, and W-band in liquid and frozen toluene, ethanol and ionic liquid solutions. Variations of the intramolecular dynamics and conformational transitions in the biradical as a function of temperature in the range of 240–420 K, polarity and the ionic strength were characterized by changes in the isotropic 14N hyperfine splitting (hfs) constant a, values of the exchange integral |J|, and the empirical parameter γ3, the ratio between conformations with slow and fast transitions. Thermodynamic parameters of the conformational rearrangements are calculated. The obtained results were compared with the X-ray structural data and quantum chemical calculations of the geometries and intramolecular transitions of biradical BS. Possible mechanisms of the polarity and the ionic strength effect on the biradical behavior in solutions of different types are discussed.

Kokorin A.I. , Mladenova-Kattnig B.Y. , Gromov O.I. , Shubin A.A. , Zaripov R.B. , Grampp G.
Influence of Polarity and Ionic Strength on Intramolecular Spin Exchange in a Short Nitroxide Biradical, Containing Sulphur Atom in the Bridge
Applied Magnetic Resonance. 2018. V.49. N10. P.1059-1073. DOI: 10.1007/s00723-018-1041-y WOS Scopus РИНЦ AN OpenAlex

Submitted:	May 18, 2018
Published online:	Jul 17, 2018
Published print:	Oct 1, 2018

Web of science:	WOS:000444236900002
Scopus:	2-s2.0-85049998790
Elibrary:	35757493
Chemical Abstracts:	2018:1362022
OpenAlex:	W2885002796

DB	Citing
Web of science	3
Scopus	3
Elibrary	3
OpenAlex	2