Cationic and anionic environments in mono-urethanesil hybrids doped with magnesium triflate
authors Goncalves, MC; Bermudez, VD; Ostrovskii, D; Carlos, LD
nationality International
journal SOLID STATE IONICS
author keywords mono-urethanesils; magnesium triflate; FT-IR; FT-Raman
keywords GEL POLYMER ELECTROLYTE; SHORT POLYETHER CHAINS; POLY(ETHYLENE OXIDE); INFRARED TEMPERATURE; IONIC INTERACTIONS; TRIVALENT CATIONS; COMPLEXES; STATE; PEO; COORDINATION
abstract Sol-gel derived poly(oxyethylene), POE/siloxane hybrids (mono-urethanesils) with a wide range of magnesium triflate (Mg(CF3SO3)(2)) concentrations were analyzed by infrared and Raman spectroscopies with the goal of examining the cation/polymer, cation/cross-link, hydrogen bonding and cation/anion interactions. In the host matrix of these xerogels short CH3-terminated POE segments are covalently bonded to the siliceous backbone through urethane linkages. Samples with infinity > n greater than or equal to 6 (where n is the molar ratio of (OCH2CH2) moieties per Mg2+ ion) were synthesized. The spectral data obtained provided conclusive evidence that the ether oxygen atoms of the polymer chains of the host structure complex the alkaline-earth ions in materials with n less than or equal to 60. "Free" triflate ions and weakly coordinated anions were detected over the whole range of salt concentration examined. The coordinated triflate species are formed in two different bonding environments. Contact ion pairs appear in materials with n less than or equal to 60. This work confirms previous studies that suggested that the nature of the cations added to the mono-urethanesil-type framework plays a key-role in the properties of these composites. (C) 2003 Elsevier B.V. All rights reserved.
publisher ELSEVIER SCIENCE BV
issn 0167-2738
year published 2004
volume 166
issue 1-2
beginning page 103
ending page 114
digital object identifier (doi) 10.1016/j.ssi.2003.11.003
web of science category Chemistry, Physical; Physics, Condensed Matter
subject category Chemistry; Physics
unique article identifier WOS:000220610200013
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