Evidence for Indirect Action of Ionizing Radiation in 18-Crown-6 Complexes with Halogenous Salts of Strontium: Simulation of Radiation-Induced Transformations in Ionic Liquid/Crown Ether Compositions

Ionic liquid/crown ether compositions are an attractive alternative to traditional extractants in the processes for spent nuclear fuel and liquid radioactive wastes reprocessing. These compositions are exposed to ionizing radiation, and their radiation stability, especially in the presence of metal salts, is a crucial issue. In the present study, the macrocyclic 18C6·Sr(BF4)2 and 18C6·Sr(PF6)2 complexes simulating the components of metal loaded ionic liquid/crown ether extractants were synthesized and their structures were characterized by FTIR spectroscopy and single-crystal X-ray diffraction analysis. Inclusion of Sr2+ cation into the 18C6 cavity resulted in more symmetric D3d conformations of the macrocycle. The structural transformations of the crown ether were accompanied by an elongation of polyether C - O bonds that could increase the possibility of radiolytic cleavage of the macrocycle. However, EPR study of the synthesized compounds subjected to X-ray irradiation revealed predominant formation of macrocyclic -CH2-ĊH-O- radicals. This result demonstrated an evidence for indirect action of ionizing radiation on individual components of the complexes and was reasonably described by a positive "hole" transfer from primary macrocyclic radical cation to fluorous anion at the primary stages of radiolysis and a subsequent interaction of fluorine atom with 18C6 macrocycle in secondary radical reactions. The observed effects may be partially responsible for enhanced sensitivity of the ionic liquid/crown ether extractants to ionizing radiation due to chemical blocking of the crown ether with radiolytic HF, radiation-chemical degradation of the 18C6, and precipitation of a low-soluble SrF2. © 2018 American Chemical Society.

Zakurdaeva O.A.1 , Nesterov S.V.1, 2 , Sokolova N.A.3 , Dorovatovskii P.V.4 , Zubavichus Y.V.4 , Khrustalev V.N. 5 , Asachenko A.F. 5, 6 , Chesnokov G.A.2, 6 , Nechaev M.S.2, 6 , Feldman V.I.1, 2
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  • 1 Enikolopov Institute of Synthetic Polymer Materials of RAS, ul. Profsoyuznaya, 70, Moscow, 117393, Russian Federation
  • 2 Department of Chemistry, Lomonosov Moscow State University, Moscow, 119991, Russian Federation
  • 3 Zelinsky Institute of Organic Chemistry of RAS, Leninsky Prospect, 47, Moscow, 119991, Russian Federation
  • 4 NRC Kurchatov Institute, Acad. Kurchatov Sq., 1, Moscow, 123182, Russian Federation
  • 5 Peoples' Friendship University of Russia (RUDN University), ul. Miklukho-Maklay, 6, Moscow, 117198, Russian Federation
  • 6 Topchiev Institute of Petrochemical Synthesis of RAS, Leninsky Prospect, 29, Moscow, 119991, Russian Federation
Crown ethers; Ethers; Fourier transform infrared spectroscopy; Ionic liquids; Ionizing radiation; Ligands; Liquids; Nuclear fuel reprocessing; Positive ions; Precipitation (chemical); Radiation chemistry; Radiation effects; Radiation shielding; Radiolysis; Reaction kinetics; Salts; Single crystals; Synthesis (chemical); X ray diffraction analysis; Chemical degradation; Enhanced sensitivity; Individual components; Liquid radioactive wastes; Radiation stability; Single crystal X-ray diffraction analysis; Spent nuclear fuels; Structural transformation; Radiation
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