Conformational rearrangement of 18-crown-6 upon the formation of aquanitratouranyl complexes: The refinement of crystal and molecular structures for [UO2(NO3)2(H2O)2] · 2H2O · 18C6

Mikhaǐlov, Yu. N.; Свешникова, Л. Б.; Kanishcheva, A. S.; Belomestnykh, V. I.; Churakov, Andrei V.

doi:10.1134/s0036023609120092

Cited by 4 publications

(1 citation statement)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The range of 1000–800 cm –1 in the FTIR spectra of these macrocyclic complexes is more informative due to its conformational sensitivities. The rocking vibrations of the methylene groups in 18C6 macrocycle has been demonstrated to depend on a conformation of −OCH 2 CH 2 O– moiety, ,, which could be characterized with the values of torsion angles in this structural unit. In particular, an inclusion of potassium cation into 18C6 cavity is well-known to result in T–G–T-conformation of −OCH 2 CH 2 O– units ( D 3 d symmetry) that accompanies with a decrease in the number of the respective absorption bands in FTIR spectrum .…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2018

View full text Add to dashboard Cite

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(BF) and 18C6·Sr(PF) 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 Sr cation into the 18C6 cavity resulted in more symmetric D 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 -CH-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 SrF.

show abstract