Conformational insight into radiation-chemical transformations of dicyclohexano-18-crown-6 complexes with alkaline earth metal chlorides: Effect of cation size
3
Publication type: Journal Article
Publication date: 2019-11-01
scimago Q2
wos Q1
SJR: 0.543
CiteScore: 5.6
Impact factor: 3.3
ISSN: 0969806X, 18790895
Radiation
Abstract
Abstract Effects of cation size on relative yields of macrocycle cleavage under irradiation of stereoisomeric dicyclohexano-18-crown-6 complexes with alkaline earth metal chlorides were studied to mimic the radiolysis of the macrocyclic components of metal-loaded extractants applicable for radioactive waste reprocessing. Chloride-anions was found to prevent the macrocycle from destruction at early stage of radiolysis. However, radiolytic atomic chlorine was generated as a result of anion decay that promoted radiation-chemical transformations of the crown ether in secondary radical reactions. Interaction of metal cation with donor oxygen atoms of crown ether led to conformational rearrangement of the macrocycle and induced additional channel of C–O bond cleavage at post-radiation stages of radiolysis. Total fraction of acyclic radical products increased as follows: Ca2+ > Sr2+ > Ba2+. This sequence order is correlated with data of vibrational spectroscopy and implies more radiation sensitivity of the folded, asymmetric conformation of macrocycle in complexes with calcium chloride in contrast to symmetric complexes with barium chloride.
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Nesterov S. et al. Conformational insight into radiation-chemical transformations of dicyclohexano-18-crown-6 complexes with alkaline earth metal chlorides: Effect of cation size // Radiation Physics and Chemistry. 2019. Vol. 164. p. 108368.
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Nesterov S., Zakurdaeva O. A., Sokolova N. A., Rudakova T. A., Feldman V. I. Conformational insight into radiation-chemical transformations of dicyclohexano-18-crown-6 complexes with alkaline earth metal chlorides: Effect of cation size // Radiation Physics and Chemistry. 2019. Vol. 164. p. 108368.
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TY - JOUR
DO - 10.1016/j.radphyschem.2019.108368
UR - https://linkinghub.elsevier.com/retrieve/pii/S0969806X1930427X
TI - Conformational insight into radiation-chemical transformations of dicyclohexano-18-crown-6 complexes with alkaline earth metal chlorides: Effect of cation size
T2 - Radiation Physics and Chemistry
AU - Nesterov, Sergey
AU - Zakurdaeva, Olga A
AU - Sokolova, Natalya A
AU - Rudakova, Tatyana A
AU - Feldman, Vladimir I.
PY - 2019
DA - 2019/11/01
PB - Elsevier
SP - 108368
VL - 164
SN - 0969-806X
SN - 1879-0895
ER -
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@article{2019_Nesterov,
author = {Sergey Nesterov and Olga A Zakurdaeva and Natalya A Sokolova and Tatyana A Rudakova and Vladimir I. Feldman},
title = {Conformational insight into radiation-chemical transformations of dicyclohexano-18-crown-6 complexes with alkaline earth metal chlorides: Effect of cation size},
journal = {Radiation Physics and Chemistry},
year = {2019},
volume = {164},
publisher = {Elsevier},
month = {nov},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0969806X1930427X},
pages = {108368},
doi = {10.1016/j.radphyschem.2019.108368}
}