Ion conducting and paramagnetic d-PCL(530)/siloxane-based biohybrids doped with Mn2+ ions
authors Pereira, RFP; Donoso, JP; Magon, CJ; Silva, IDA; Cardoso, MA; Goncalves, MC; Sabadini, RC; Pawlicka, A; Bermudez, VD; Silva, MM
nationality International
journal ELECTROCHIMICA ACTA
author keywords poly(e-caprolactone)/siloxane biohybrids; manganese perchlorate; sol-gel; ionic conductivity; paramagnetism
keywords ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY; ELECTROCHROMIC DEVICES; MANGANESE IONS; LITHIUM PERCHLORATE; SMART WINDOWS; DI-UREASILS; X-RAY; ELECTROLYTES; GLASSES; GREEN
abstract Amorphous poly(epsilon-caprolactone) (PCL(530))/siloxane ormolytes doped with manganese perchlorate (Mn(ClO4)(2)) (d-PCL(530)/siloxane(n)Mn(ClO4)(2) with n = 20, 50, and 100), thermally stable up to at least 200 degrees C, were synthesized by the sol-gel method. Ionic conductivity values up to 4.8 x 10(-8) and 2.0 x 10(-6) S cm(-1) at about 25 and 100 degrees C, respectively, were obtained for n = 20. FT-IR data demonstrated that the hydrogen bonding interactions present in the non-doped d-PCL(530)/siloxane host hybrid matrix were significantly influenced by the inclusion of Mn(ClO4)(2) which promoted the formation of more oxyethylene/urethane and urethane/urethane aggregates. In addition, the Mn2+ ions bonded to all the "free" C = O groups of the urethane cross-links and to some of the "free" ester groups of the amorphous PCL(530) chains. In the electrolytes, the ClO4- ions were found "free" and bonded to the Mn2+ ions along a bidentate configuration. The magnitude of the electron paramagnetic resonance (EPR) hyperfine constant of the analyzed samples (A approximate to 90 x 10(-4)cm(-1)) suggested that the bonding between Mn2+ ions and the surrounding ligands is moderately ionic. The synthetized d-PCL(530)/siloxanenMn (ClO4)(2) biohybrids have potential application in paramagnetic, photoelectrochemical and electrochromic devices. (C) 2016 Elsevier Ltd. All rights reserved.
publisher PERGAMON-ELSEVIER SCIENCE LTD
issn 0013-4686
year published 2016
volume 211
beginning page 804
ending page 813
digital object identifier (doi) 10.1016/j.electacta.2016.06.088
web of science category Electrochemistry
subject category Electrochemistry
unique article identifier WOS:000380904100092
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