{"title":"基于未知Zr8/Hf8立方簇的金属有机骨架","authors":"Dawei Feng, Hai-Long Jiang, Ying-Pin Chen, Zhi-Yuan Gu, Zhangwen Wei, Hong-Cai Zhou*","doi":"10.1021/ic4018536","DOIUrl":null,"url":null,"abstract":"<p >The ongoing study of zirconium– and hafnium–porphyrinic metal–organic frameworks (MOFs) led to the discovery of isostructural MOFs based on Zr<sub>8</sub> and Hf<sub>8</sub> clusters, which are unknown in both cluster and MOF chemistry. The Zr<sub>8</sub>O<sub>6</sub> cluster features an idealized Zr<sub>8</sub> cube, in which each Zr atom resides on one vertex and each face of the cube is capped by one μ<sub>4</sub>-oxygen atom. On each edge of the cube, a carboxylate from a porphyrinic ligand bridges two Zr atoms to afford a 3D MOF with a very rare (4,12)-connected <b>ftw</b> topology, in which two types of polyhedral cages with diameters of ～1.1 and ～2.0 nm and a cage opening of ～0.8 nm are found. The isostructural Zr– and Hf–MOFs exhibit high surface areas, gas uptakes, and catalytic selectivity for cyclohexane oxidation.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"52 21","pages":"12661–12667"},"PeriodicalIF":4.7000,"publicationDate":"2013-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1021/ic4018536","citationCount":"176","resultStr":"{\"title\":\"Metal–Organic Frameworks Based on Previously Unknown Zr8/Hf8 Cubic Clusters\",\"authors\":\"Dawei Feng, Hai-Long Jiang, Ying-Pin Chen, Zhi-Yuan Gu, Zhangwen Wei, Hong-Cai Zhou*\",\"doi\":\"10.1021/ic4018536\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The ongoing study of zirconium– and hafnium–porphyrinic metal–organic frameworks (MOFs) led to the discovery of isostructural MOFs based on Zr<sub>8</sub> and Hf<sub>8</sub> clusters, which are unknown in both cluster and MOF chemistry. The Zr<sub>8</sub>O<sub>6</sub> cluster features an idealized Zr<sub>8</sub> cube, in which each Zr atom resides on one vertex and each face of the cube is capped by one μ<sub>4</sub>-oxygen atom. On each edge of the cube, a carboxylate from a porphyrinic ligand bridges two Zr atoms to afford a 3D MOF with a very rare (4,12)-connected <b>ftw</b> topology, in which two types of polyhedral cages with diameters of ～1.1 and ～2.0 nm and a cage opening of ～0.8 nm are found. The isostructural Zr– and Hf–MOFs exhibit high surface areas, gas uptakes, and catalytic selectivity for cyclohexane oxidation.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"52 21\",\"pages\":\"12661–12667\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2013-10-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1021/ic4018536\",\"citationCount\":\"176\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/ic4018536\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/ic4018536","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Metal–Organic Frameworks Based on Previously Unknown Zr8/Hf8 Cubic Clusters
The ongoing study of zirconium– and hafnium–porphyrinic metal–organic frameworks (MOFs) led to the discovery of isostructural MOFs based on Zr8 and Hf8 clusters, which are unknown in both cluster and MOF chemistry. The Zr8O6 cluster features an idealized Zr8 cube, in which each Zr atom resides on one vertex and each face of the cube is capped by one μ4-oxygen atom. On each edge of the cube, a carboxylate from a porphyrinic ligand bridges two Zr atoms to afford a 3D MOF with a very rare (4,12)-connected ftw topology, in which two types of polyhedral cages with diameters of ～1.1 and ～2.0 nm and a cage opening of ～0.8 nm are found. The isostructural Zr– and Hf–MOFs exhibit high surface areas, gas uptakes, and catalytic selectivity for cyclohexane oxidation.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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