{"title":"具有新型六角 A4B2C 隧道结构的新型高能十二氢共十二硼酸盐 (N2H5)4X2[B12H12] (X = Cl 和 Br)","authors":"Rouzbeh Aghaei Hakkak, Thomas Schleid","doi":"10.1021/acs.chemmater.4c02058","DOIUrl":null,"url":null,"abstract":"Two new tetrahydrazinium dihalide dodecahydro-<i>closo</i>-dodecaborates (N<sub>2</sub>H<sub>5</sub>)<sub>4</sub><i>X</i><sub>2</sub>[B<sub>12</sub>H<sub>12</sub>] (<i>X</i><sup>–</sup> = Cl<sup>–</sup> and Br<sup>–</sup>) were successfully synthesized via the direct reaction of dihydrazinium dodecahydro-<i>closo</i>-dodecaborate (N<sub>2</sub>H<sub>4</sub>)<sub>2</sub>[B<sub>12</sub>H<sub>12</sub>] with hydrazinium halides (N<sub>2</sub>H<sub>5</sub>)Cl and (N<sub>2</sub>H<sub>5</sub>)Br in aqueous media. The resulting isotypic compounds crystallize monoclinically in the space group <i>P</i>2<sub>1</sub>/<i>c</i> with similar unit-cell parameters (<i>a</i> = 681.98(4) pm, <i>b</i> = 1025.38(6) pm, <i>c</i> = 1325.38(8) pm, and β = 98.393(3)° for the chloride and <i>a</i> = 686.05(4) pm, <i>b</i> = 1032.51(6) pm, <i>c</i> = 1316.04(8), and β = 97.449(3)° for the bromide). Their crystal structure was elucidated using single-crystal X-ray diffraction techniques, unveiling a new unique arrangement for the composition <i>A</i><sub>4</sub><i>B</i><sub>2</sub><i>C</i> (<i>A</i> = hydrazinium, <i>B</i> = halide, and <i>C</i> = dodecahydro-<i>closo</i>-dodecaborate). This distinctive structural configuration sets it apart from compounds exhibiting other <i>A</i><sub>4</sub><i>B</i><sub>2</sub><i>C</i> arrangements, such as the spinel or double-perovskite structure type. In this new structure, the halide anions are coordinated by five hydrazinium cations, creating triangular bipyramidal polyhedra. These are interconnected via edge- and corner-sharing, resulting in the formation of hexagonal tunnels along the [100] direction. Within each of these tunnels, the [B<sub>12</sub>H<sub>12</sub>]<sup>2–</sup> clusters reside centrally located. Differential scanning calorimetry analyses demonstrate that these compounds contain a substantial amount of energy that is released during their thermal decomposition.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 1","pages":""},"PeriodicalIF":7.2000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"New Energetic Dodecahydro-closo-Dodecaborates (N2H5)4X2[B12H12] (X = Cl and Br) with a Novel Hexagonal A4B2C Tunnel Structure\",\"authors\":\"Rouzbeh Aghaei Hakkak, Thomas Schleid\",\"doi\":\"10.1021/acs.chemmater.4c02058\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Two new tetrahydrazinium dihalide dodecahydro-<i>closo</i>-dodecaborates (N<sub>2</sub>H<sub>5</sub>)<sub>4</sub><i>X</i><sub>2</sub>[B<sub>12</sub>H<sub>12</sub>] (<i>X</i><sup>–</sup> = Cl<sup>–</sup> and Br<sup>–</sup>) were successfully synthesized via the direct reaction of dihydrazinium dodecahydro-<i>closo</i>-dodecaborate (N<sub>2</sub>H<sub>4</sub>)<sub>2</sub>[B<sub>12</sub>H<sub>12</sub>] with hydrazinium halides (N<sub>2</sub>H<sub>5</sub>)Cl and (N<sub>2</sub>H<sub>5</sub>)Br in aqueous media. The resulting isotypic compounds crystallize monoclinically in the space group <i>P</i>2<sub>1</sub>/<i>c</i> with similar unit-cell parameters (<i>a</i> = 681.98(4) pm, <i>b</i> = 1025.38(6) pm, <i>c</i> = 1325.38(8) pm, and β = 98.393(3)° for the chloride and <i>a</i> = 686.05(4) pm, <i>b</i> = 1032.51(6) pm, <i>c</i> = 1316.04(8), and β = 97.449(3)° for the bromide). Their crystal structure was elucidated using single-crystal X-ray diffraction techniques, unveiling a new unique arrangement for the composition <i>A</i><sub>4</sub><i>B</i><sub>2</sub><i>C</i> (<i>A</i> = hydrazinium, <i>B</i> = halide, and <i>C</i> = dodecahydro-<i>closo</i>-dodecaborate). This distinctive structural configuration sets it apart from compounds exhibiting other <i>A</i><sub>4</sub><i>B</i><sub>2</sub><i>C</i> arrangements, such as the spinel or double-perovskite structure type. In this new structure, the halide anions are coordinated by five hydrazinium cations, creating triangular bipyramidal polyhedra. These are interconnected via edge- and corner-sharing, resulting in the formation of hexagonal tunnels along the [100] direction. Within each of these tunnels, the [B<sub>12</sub>H<sub>12</sub>]<sup>2–</sup> clusters reside centrally located. Differential scanning calorimetry analyses demonstrate that these compounds contain a substantial amount of energy that is released during their thermal decomposition.\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":\"37 1\",\"pages\":\"\"},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-11-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.chemmater.4c02058\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acs.chemmater.4c02058","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
New Energetic Dodecahydro-closo-Dodecaborates (N2H5)4X2[B12H12] (X = Cl and Br) with a Novel Hexagonal A4B2C Tunnel Structure
Two new tetrahydrazinium dihalide dodecahydro-closo-dodecaborates (N2H5)4X2[B12H12] (X– = Cl– and Br–) were successfully synthesized via the direct reaction of dihydrazinium dodecahydro-closo-dodecaborate (N2H4)2[B12H12] with hydrazinium halides (N2H5)Cl and (N2H5)Br in aqueous media. The resulting isotypic compounds crystallize monoclinically in the space group P21/c with similar unit-cell parameters (a = 681.98(4) pm, b = 1025.38(6) pm, c = 1325.38(8) pm, and β = 98.393(3)° for the chloride and a = 686.05(4) pm, b = 1032.51(6) pm, c = 1316.04(8), and β = 97.449(3)° for the bromide). Their crystal structure was elucidated using single-crystal X-ray diffraction techniques, unveiling a new unique arrangement for the composition A4B2C (A = hydrazinium, B = halide, and C = dodecahydro-closo-dodecaborate). This distinctive structural configuration sets it apart from compounds exhibiting other A4B2C arrangements, such as the spinel or double-perovskite structure type. In this new structure, the halide anions are coordinated by five hydrazinium cations, creating triangular bipyramidal polyhedra. These are interconnected via edge- and corner-sharing, resulting in the formation of hexagonal tunnels along the [100] direction. Within each of these tunnels, the [B12H12]2– clusters reside centrally located. Differential scanning calorimetry analyses demonstrate that these compounds contain a substantial amount of energy that is released during their thermal decomposition.
期刊介绍：
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.
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