Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations
Crystals with layered structures are crucial for the construction of functional materials exhibiting intercalation, ionic conductivity, or emission properties. Polyoxometalate crystals hybridized with surfactant cations have distinct layered packings due to the surfactants which can form lamellar st...
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MDPI AG
2022-03-01
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| Online Access: | https://www.mdpi.com/1996-1944/15/7/2429 |
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| author | Jun Kobayashi Keisuke Shimura Keisuke Mikurube Saki Otobe Takashi Matsumoto Eri Ishikawa Haruo Naruke Takeru Ito |
| author_facet | Jun Kobayashi Keisuke Shimura Keisuke Mikurube Saki Otobe Takashi Matsumoto Eri Ishikawa Haruo Naruke Takeru Ito |
| author_sort | Jun Kobayashi |
| collection | DOAJ |
| description | Crystals with layered structures are crucial for the construction of functional materials exhibiting intercalation, ionic conductivity, or emission properties. Polyoxometalate crystals hybridized with surfactant cations have distinct layered packings due to the surfactants which can form lamellar structures. Introducing metal cations into such polyoxometalate-surfactant hybrid crystals is significant for the addition of specific functions. Here, polyoxomolybdate–surfactant hybrid crystals were synthesized as single crystals, and unambiguously characterized by X-ray structure analyses. Octamolybdate ([Mo<sub>8</sub>O<sub>26</sub>]<sup>4–</sup>, Mo<sub>8</sub>) and heterocyclic surfactant of 1-dodecylpyridinium (C<sub>12</sub>py) were employed. The hybrid crystals were composed of α-type and β-type Mo<sub>8</sub> isomers. Two crystalline phases containing α-type Mo<sub>8</sub> were obtained as pseudopolymorphs depending on the crystallization conditions. Crystallization with the presence of rubidium and cesium cations caused the formation of metal cation-introduced hybrid crystals comprising β-Mo<sub>8</sub> (C<sub>12</sub>py-Rb-Mo<sub>8</sub> and C<sub>12</sub>py-Cs-Mo<sub>8</sub>). The yield of the C<sub>12</sub>py-Rb-Mo<sub>8</sub> hybrid crystal was almost constant within crystallization temperatures of 279–303 K, while that of C<sub>12</sub>py-Cs-Mo<sub>8</sub> decreased over 288 K. This means that the C<sub>12</sub>py-Mo<sub>8</sub> hybrid crystal can capture Rb<sup>+</sup> and Cs<sup>+</sup> from the solution phase into the solids as the C<sub>12</sub>py-Rb-Mo<sub>8</sub> and C<sub>12</sub>py-Cs-Mo<sub>8</sub> hybrid crystals. The C<sub>12</sub>py-Mo<sub>8</sub> hybrid crystals could be applied to ion-capturing materials for heavy metal cation removal. |
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| id | doaj.art-f7d2164612c54019a0919af3f9b5203a |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
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| spelling | doaj.art-f7d2164612c54019a0919af3f9b5203a2023-11-30T23:32:02ZengMDPI AGMaterials1996-19442022-03-01157242910.3390/ma15072429Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal CationsJun Kobayashi0Keisuke Shimura1Keisuke Mikurube2Saki Otobe3Takashi Matsumoto4Eri Ishikawa5Haruo Naruke6Takeru Ito7Department of Chemistry, School of Science, Tokai University, Kanagawa 259-1292, JapanDepartment of Chemistry, School of Science, Tokai University, Kanagawa 259-1292, JapanDepartment of Chemistry, School of Science, Tokai University, Kanagawa 259-1292, JapanDepartment of Chemistry, School of Science, Tokai University, Kanagawa 259-1292, JapanApplication Laboratories, Rigaku Corporation, Tokyo 196-8666, JapanDepartment of Applied Chemistry, College of Engineering, Chubu University, Aichi 487-8501, JapanChemical Resources Laboratory, Tokyo Institute of Technology, Kanagawa 226-8503, JapanDepartment of Chemistry, School of Science, Tokai University, Kanagawa 259-1292, JapanCrystals with layered structures are crucial for the construction of functional materials exhibiting intercalation, ionic conductivity, or emission properties. Polyoxometalate crystals hybridized with surfactant cations have distinct layered packings due to the surfactants which can form lamellar structures. Introducing metal cations into such polyoxometalate-surfactant hybrid crystals is significant for the addition of specific functions. Here, polyoxomolybdate–surfactant hybrid crystals were synthesized as single crystals, and unambiguously characterized by X-ray structure analyses. Octamolybdate ([Mo<sub>8</sub>O<sub>26</sub>]<sup>4–</sup>, Mo<sub>8</sub>) and heterocyclic surfactant of 1-dodecylpyridinium (C<sub>12</sub>py) were employed. The hybrid crystals were composed of α-type and β-type Mo<sub>8</sub> isomers. Two crystalline phases containing α-type Mo<sub>8</sub> were obtained as pseudopolymorphs depending on the crystallization conditions. Crystallization with the presence of rubidium and cesium cations caused the formation of metal cation-introduced hybrid crystals comprising β-Mo<sub>8</sub> (C<sub>12</sub>py-Rb-Mo<sub>8</sub> and C<sub>12</sub>py-Cs-Mo<sub>8</sub>). The yield of the C<sub>12</sub>py-Rb-Mo<sub>8</sub> hybrid crystal was almost constant within crystallization temperatures of 279–303 K, while that of C<sub>12</sub>py-Cs-Mo<sub>8</sub> decreased over 288 K. This means that the C<sub>12</sub>py-Mo<sub>8</sub> hybrid crystal can capture Rb<sup>+</sup> and Cs<sup>+</sup> from the solution phase into the solids as the C<sub>12</sub>py-Rb-Mo<sub>8</sub> and C<sub>12</sub>py-Cs-Mo<sub>8</sub> hybrid crystals. The C<sub>12</sub>py-Mo<sub>8</sub> hybrid crystals could be applied to ion-capturing materials for heavy metal cation removal.https://www.mdpi.com/1996-1944/15/7/2429polyoxometalateinorganic-organic hybridlayered crystalsurfactantmetal cation |
| spellingShingle | Jun Kobayashi Keisuke Shimura Keisuke Mikurube Saki Otobe Takashi Matsumoto Eri Ishikawa Haruo Naruke Takeru Ito Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations Materials polyoxometalate inorganic-organic hybrid layered crystal surfactant metal cation |
| title | Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations |
| title_full | Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations |
| title_fullStr | Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations |
| title_full_unstemmed | Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations |
| title_short | Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations |
| title_sort | polyoxomolybdate layered crystals constructed from a heterocyclic surfactant syntheses pseudopolymorphism and introduction of metal cations |
| topic | polyoxometalate inorganic-organic hybrid layered crystal surfactant metal cation |
| url | https://www.mdpi.com/1996-1944/15/7/2429 |
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