Dunatov, Marko; Molčanov, Krešimir; Štefanić, Zoran; Kruk, Robert; Androš Dubraja, Lidija (2023) Interfacial Water Molecules as Agents for Phase Change Control and Proton Conductivity Enhancement in the Ammonium Vanadyl Tartrate System. Inorganic Chemistry, 63 (1). pp. 163-172. ISSN 1520-510X
Abstract
This study demonstrates the reversible structural transformation, single-crystal-to-single-crystal, of the ammonium vanadyl (L-tartrate) complex salt from the hydrate phase to the anhydrous phase. The transformation can be initiated by stimuli, such as temperature, humidity, or vacuum conditions. The hydrate and anhydrous phases exhibit a tetragonal structure (P41212), with marked differences in hydrogen bonding due to the presence or absence of one water molecule per asymmetric unit. The intricate relationship between crystal packing and intermolecular interactions in the hydrate phase was investigated by crystallographic charge density analysis revealing, at the molecular level, the reasons for the observed 5 orders of magnitude higher proton conductivity of the hydrate phase compared to that of the anhydrous phase. To gain further insight into the processes occurring at the surfaces of grain boundaries and the proton transfer mechanisms in this system, rehydration of the complex salt was carried out by using D2O instead of H2O and monitored by in situ ATR-FTIR spectroscopy. The results highlight the critical role of interfacial water molecules in driving structural transformations and influencing proton conductivity.
| Item Type: | Article | ||||||||
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| Additional Information: | This document is the Accepted Manuscript version of a Published Article that appeared in final form in Inorganic Chemistry, copyright © 2026 American Chemical Society. To access the final published article, see ACS Articles on Request. | ||||||||
| Uncontrolled Keywords: | cations; water layers; phase transitions; solvates; proton conductivity | ||||||||
| Subjects: | NATURAL SCIENCES > Chemistry NATURAL SCIENCES > Chemistry > Inorganic Chemistry |
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| Divisions: | Division of Materials Chemistry | ||||||||
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| Depositing User: | Lidija Androš Dubraja | ||||||||
| Date Deposited: | 20 Jan 2026 10:27 | ||||||||
| URI: | http://fulir.irb.hr/id/eprint/10988 | ||||||||
| DOI: | 10.1021/acs.inorgchem.3c02605 |
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