Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer
An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH<sub>3</sub>)<sub>4</sub>]MoO<sub>4</sub><b>@</b>2H<sub>2</sub>O (compound <b>1</b><b>@</b>2H<sub>2</sub>O) with the formation...
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-06-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/13/4022 |
| _version_ | 1797528155572928512 |
|---|---|
| author | Kende Attila Béres István E. Sajó György Lendvay László Trif Vladimir M. Petruševski Berta Barta-Holló László Korecz Fernanda Paiva Franguelli Krisztina László Imre Miklós Szilágyi László Kótai |
| author_facet | Kende Attila Béres István E. Sajó György Lendvay László Trif Vladimir M. Petruševski Berta Barta-Holló László Korecz Fernanda Paiva Franguelli Krisztina László Imre Miklós Szilágyi László Kótai |
| author_sort | Kende Attila Béres |
| collection | DOAJ |
| description | An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH<sub>3</sub>)<sub>4</sub>]MoO<sub>4</sub><b>@</b>2H<sub>2</sub>O (compound <b>1</b><b>@</b>2H<sub>2</sub>O) with the formation of [(NH<sub>4</sub>)<i><sub>x</sub></i>H<sub>(1−<i>x</i>)</sub>Zn(OH)(MoO<sub>4</sub>)]<sub>n</sub> (x = 0.92–0.94) coordination polymer (formally NH<sub>4</sub>Zn(OH)MoO<sub>4</sub>, compound <b>2</b>) is described. Based on the isostructural relationship, the powder XRD indicates that the crystal lattice of compound <b>1@</b>2H<sub>2</sub>O contains a hydrogen-bonded network of tetraamminezinc (2+) and molybdate (2−) ions, and there are cavities (O<sub>4</sub>N<sub>4</sub>(μ-H<sub>12</sub>) 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 <b>@</b> symbol in the notation is intended to emphasize that the H<sub>2</sub>O 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 <b>1@</b>2H<sub>2</sub>O easily releases its water content even on standing and yields compound <b>2</b>. Surprisingly, hydrolysis products of <b>1</b> 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 <b>2</b> (<b>2</b>#dotCu) showed that this complex consists of two different Cu<sup>2+</sup>(Zn<sup>2+</sup>) environments in the polymeric structure. Thermal decomposition of compounds <b>1</b> and <b>2</b> results in ZnMoO<sub>4</sub> with similar specific surface area and morphology. The ZnMoO<sub>4</sub> samples prepared from compounds <b>1</b> and <b>2</b> and compound <b>2</b> in itself are active photocatalysts in the degradation of Congo Red dye. IR, Raman, and UV studies on compounds <b>1@</b>2H<sub>2</sub>O and <b>2</b> are discussed in detail. |
| first_indexed | 2024-03-10T09:54:09Z |
| format | Article |
| id | doaj.art-c95262ee0e874f49b1fb2f9958b315e2 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T09:54:09Z |
| publishDate | 2021-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-c95262ee0e874f49b1fb2f9958b315e22023-11-22T02:31:51ZengMDPI AGMolecules1420-30492021-06-012613402210.3390/molecules26134022Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination PolymerKende Attila Béres0István E. Sajó1György Lendvay2László Trif3Vladimir M. Petruševski4Berta Barta-Holló5László Korecz6Fernanda Paiva Franguelli7Krisztina László8Imre Miklós Szilágyi9László Kótai10Research Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, HungarySzentagothai Research Centre, Environmental Analytical and Geoanalytical Research Group, University of Pécs, Ifjúság Útja 20, 7624 Pécs, HungaryResearch Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, HungaryResearch Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, HungaryFaculty of Natural Sciences and Mathematics, Ss. Cyryl and Methodius University, 1000 Skopje, North MacedoniaDepartment of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovica 3, 21000 Novi Sad, SerbiaResearch Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, HungaryResearch Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, HungaryDepartment of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, Műegyetem Rakpart 3, 1111 Budapest, HungaryDepartment of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Műegyetem Rakpart 3, 1111 Budapest, HungaryResearch Centre for Natural Sciences, Magyar Tudósok Krt 2, 1117 Budapest, HungaryAn aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH<sub>3</sub>)<sub>4</sub>]MoO<sub>4</sub><b>@</b>2H<sub>2</sub>O (compound <b>1</b><b>@</b>2H<sub>2</sub>O) with the formation of [(NH<sub>4</sub>)<i><sub>x</sub></i>H<sub>(1−<i>x</i>)</sub>Zn(OH)(MoO<sub>4</sub>)]<sub>n</sub> (x = 0.92–0.94) coordination polymer (formally NH<sub>4</sub>Zn(OH)MoO<sub>4</sub>, compound <b>2</b>) is described. Based on the isostructural relationship, the powder XRD indicates that the crystal lattice of compound <b>1@</b>2H<sub>2</sub>O contains a hydrogen-bonded network of tetraamminezinc (2+) and molybdate (2−) ions, and there are cavities (O<sub>4</sub>N<sub>4</sub>(μ-H<sub>12</sub>) 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 <b>@</b> symbol in the notation is intended to emphasize that the H<sub>2</sub>O 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 <b>1@</b>2H<sub>2</sub>O easily releases its water content even on standing and yields compound <b>2</b>. Surprisingly, hydrolysis products of <b>1</b> 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 <b>2</b> (<b>2</b>#dotCu) showed that this complex consists of two different Cu<sup>2+</sup>(Zn<sup>2+</sup>) environments in the polymeric structure. Thermal decomposition of compounds <b>1</b> and <b>2</b> results in ZnMoO<sub>4</sub> with similar specific surface area and morphology. The ZnMoO<sub>4</sub> samples prepared from compounds <b>1</b> and <b>2</b> and compound <b>2</b> in itself are active photocatalysts in the degradation of Congo Red dye. IR, Raman, and UV studies on compounds <b>1@</b>2H<sub>2</sub>O and <b>2</b> are discussed in detail.https://www.mdpi.com/1420-3049/26/13/4022amminehydrolysisvibrational spectroscopythermal analysiszinc molybdatephotocatalysis |
| spellingShingle | Kende Attila Béres István E. Sajó György Lendvay László Trif Vladimir M. Petruševski Berta Barta-Holló László Korecz Fernanda Paiva Franguelli Krisztina László Imre Miklós Szilágyi László Kótai Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer Molecules ammine hydrolysis vibrational spectroscopy thermal analysis zinc molybdate photocatalysis |
| title | Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer |
| title_full | Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer |
| title_fullStr | Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer |
| title_full_unstemmed | Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer |
| title_short | Solid-Phase “Self-Hydrolysis” of [Zn(NH<sub>3</sub>)<sub>4</sub>MoO<sub>4</sub>@2H<sub>2</sub>O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer |
| title_sort | solid phase self hydrolysis of zn nh sub 3 sub sub 4 sub moo sub 4 sub 2h sub 2 sub o involving enclathrated water an easy route to a layered basic ammonium zinc molybdate coordination polymer |
| topic | ammine hydrolysis vibrational spectroscopy thermal analysis zinc molybdate photocatalysis |
| url | https://www.mdpi.com/1420-3049/26/13/4022 |
| work_keys_str_mv | AT kendeattilaberes solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT istvanesajo solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT gyorgylendvay solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT laszlotrif solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT vladimirmpetrusevski solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT bertabartahollo solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT laszlokorecz solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT fernandapaivafranguelli solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT krisztinalaszlo solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT imremiklosszilagyi solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer AT laszlokotai solidphaseselfhydrolysisofznnhsub3subsub4submoosub4sub2hsub2suboinvolvingenclathratedwateraneasyroutetoalayeredbasicammoniumzincmolybdatecoordinationpolymer |