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Chemical and Electrochemical Alkali Cations Intercalation/Release in an Ionic Hydrogen Bonded Network
journal contribution
posted on 2019-01-10, 20:50 authored by Geoffrey Gerer, Frédéric Melin, Petra Hellwig, Mir Wais Hosseini, Sylvie FerlayThe
chemical oxidation of a hydrogen bonded network, formed upon
combination of a hydrogen bond donor dication (12+, a dicationic bis-amidinium organic moiety bearing four
propyl chains) with [FeIII/II(CN)6]3–/4– anions has been studied using vibrational spectroscopies. The postsynthetic
oxidation of the microcrystalline powder of X213-[FeII(CN)6]2 (X = Na,
K, and Cs) by S2O82– into 13-[FeIII(CN)6]2 appeared to be partial for X = K+ and Cs+ and
total for Na213-[FeII(CN)6]2. It corresponds to a two-step process
involving a second order reaction. The reaction time appears to be
dependent on the nature of the alkali cation and is faster for X =
Na+. The integrity of the hydrogen bonded network, after
oxidation, was also confirmed by powder X-ray diffraction. The flexible
nature of the hydrogen bonded network allows alkali cation motions
within the network during the oxidation process. In addition, the
investigation of the electrochemical behavior evidenced an amorphous
deposition on a gold electrode immersed into a solution containing
(12+ and [FeIII(CN)6]3–) after 100 cycles. This is the first evidence
of an electrochemical ion intercalation for a molecular hydrogen bonded
network.
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Keywords
order reactionhydrogen bond donor dicationpowder X-ray diffractionvibrational spectroscopiesdicationic bis-amidiniumFe IIIoxidation processnaturepropyl chainselectrochemical ion intercalationchemical oxidationNaIonic Hydrogen Bonded NetworkCNalkali cation motionselectrochemical behaviorreaction time100 cyclesgold electrodemicrocrystalline powderalkali cationpostsynthetic oxidation
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