|Title:||Fluoride Ion Interactions in Alkali-Metal Fluoride-Diol Complexes|
Matsumoto, Kazuhiko https://orcid.org/0000-0002-0770-9210 (unconfirmed)
Nagata, Takashi https://orcid.org/0000-0002-3733-2709 (unconfirmed)
Katahira, Masato https://orcid.org/0000-0003-0336-7660 (unconfirmed)
Hagiwara, Rika https://orcid.org/0000-0002-7234-3980 (unconfirmed)
|Author's alias:||松本, 一彦|
|Keywords:||Physical and Theoretical Chemistry|
|Publisher:||American Chemical Society|
|Journal title:||Inorganic Chemistry|
|Abstract:||The activity of F⁻ is an important factor in the design of both inorganic and organic reactions involving fluorine compounds. The present study investigates interactions of F⁻ with diols in alkali-metal fluoride–diol complexes. Increases in the reactivities of alkali-metal fluorides and their solubilities in alcohols is observed with increasing cation size. The difference in alkali-metal ion size produces different structural motifs for F⁻-diol complex salts. The CsF complex salt with ethylene glycol (EG), CsF-EG, has a layered structure, whereas the Rb and K complex salts, (RbF)₅-(EG)₄ and (KF)₅-(EG)₄, form columnar structures. Comparison of the CsF complex salts with three different diols— EG, 1, 3-propylene glycol (PG₁₃), and 1, 4-butylene glycol (PG₁₄)—revealed that the diol chain length affects the bridging mode in their layered structures. EG bridges two OH oxygen atoms within the same CsF layer in CsF-EG, whereas PG₁₃ and BG₁₄ bridge two OH oxygen atoms in different CsF layers in (CsF)₂-PG₁₃ and CsF-BG₁₄, respectively. The F⁻ ion coordination environment involves interactions between alkali-metal ions and H atom(s) in the diol OH groups, where the F⁻···H interactions are more dominant than the F···M⁺ interaction, based on Hirshfeld surface analyses. The O–H bond weakening observed by infrared spectroscopy also reflects the strengths of the F⁻···H interactions in these complex salts.|
|Rights:||This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.0c00783.|
The full-text file will be made open to the public on 22 April 2021 in accordance with publisher's 'Terms and Conditions for Self-Archiving'.
This is not the published version. Please cite only the published version.
|Appears in Collections:||Journal Articles|
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.