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Article

Solid-Phase “Self-Hydrolysis” of [Zn(NH3)4MoO4@2H2O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer

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Research Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, Hungary
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Szentagothai Research Centre, Environmental Analytical and Geoanalytical Research Group, University of Pécs, Ifjúság Útja 20, 7624 Pécs, Hungary
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Faculty of Natural Sciences and Mathematics, Ss. Cyryl and Methodius University, 1000 Skopje, North Macedonia
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Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovica 3, 21000 Novi Sad, Serbia
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Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Műegyetem Rakpart 3, 1111 Budapest, Hungary
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Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, Műegyetem Rakpart 3, 1111 Budapest, Hungary
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Deuton-X Ltd., Selmeci u. 89, 2030 Érd, Hungary
*
Author to whom correspondence should be addressed.
Academic Editors: Marina Fonari and Rodica Olar
Molecules 2021, 26(13), 4022; https://doi.org/10.3390/molecules26134022
Received: 31 May 2021 / Revised: 22 June 2021 / Accepted: 23 June 2021 / Published: 30 June 2021
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH3)4]MoO4@2H2O (compound 1@2H2O) with the formation of [(NH4)xH(1−x)Zn(OH)(MoO4)]n (x = 0.92–0.94) coordination polymer (formally NH4Zn(OH)MoO4, compound 2) is described. Based on the isostructural relationship, the powder XRD indicates that the crystal lattice of compound [email protected]2H2O contains a hydrogen-bonded network of tetraamminezinc (2+) and molybdate (2−) ions, and there are cavities (O4N4(μ-H12) cube) occupied by the two water molecules, which stabilize the crystal structure. Several observations indicate that the water molecules have no fixed positions in the lattice voids; instead, the cavity provides a neighborhood similar to those in clathrates. The @ symbol in the notation is intended to emphasize that the H2O in this compound is enclathrated rather than being water of crystallization. Yet, signs of temperature-dependent dynamic interactions with the wall of the cages can be detected, and [email protected]2H2O easily releases its water content even on standing and yields compound 2. Surprisingly, hydrolysis products of 1 were observed even in the absence of aerial humidity, which suggests a unique solid-phase quasi-intramolecular hydrolysis. A mechanism involving successive substitution of the ammonia ligands by water molecules and ammonia release is proposed. An ESR study of the Cu-doped compound 2 (2#dotCu) showed that this complex consists of two different Cu2+(Zn2+) environments in the polymeric structure. Thermal decomposition of compounds 1 and 2 results in ZnMoO4 with similar specific surface area and morphology. The ZnMoO4 samples prepared from compounds 1 and 2 and compound 2 in itself are active photocatalysts in the degradation of Congo Red dye. IR, Raman, and UV studies on compounds [email protected]2H2O and 2 are discussed in detail. View Full-Text
Keywords: ammine; hydrolysis; vibrational spectroscopy; thermal analysis; zinc molybdate; photocatalysis ammine; hydrolysis; vibrational spectroscopy; thermal analysis; zinc molybdate; photocatalysis
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MDPI and ACS Style

Béres, K.A.; Sajó, I.E.; Lendvay, G.; Trif, L.; Petruševski, V.M.; Barta-Holló, B.; Korecz, L.; Franguelli, F.P.; László, K.; Szilágyi, I.M.; Kótai, L. Solid-Phase “Self-Hydrolysis” of [Zn(NH3)4MoO4@2H2O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer. Molecules 2021, 26, 4022. https://doi.org/10.3390/molecules26134022

AMA Style

Béres KA, Sajó IE, Lendvay G, Trif L, Petruševski VM, Barta-Holló B, Korecz L, Franguelli FP, László K, Szilágyi IM, Kótai L. Solid-Phase “Self-Hydrolysis” of [Zn(NH3)4MoO4@2H2O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer. Molecules. 2021; 26(13):4022. https://doi.org/10.3390/molecules26134022

Chicago/Turabian Style

Béres, Kende A., István E. Sajó, György Lendvay, László Trif, Vladimir M. Petruševski, Berta Barta-Holló, László Korecz, Fernanda P. Franguelli, Krisztina László, Imre M. Szilágyi, and László Kótai. 2021. "Solid-Phase “Self-Hydrolysis” of [Zn(NH3)4MoO4@2H2O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer" Molecules 26, no. 13: 4022. https://doi.org/10.3390/molecules26134022

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