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通过由（1,4,7-三氮杂环壬烷）钴（III）配合物桥连的[HVO]阴离子堆叠，对模拟氧化钒层状结构的聚氧阳离子进行策略性分离。

Strategic Isolation of a Polyoxocation Mimicking Vanadium(V) Oxide Layered-Structure by Stacking of [HVO] Anions Bridged by (1,4,7-Triazacyclononane)Co(III) Complexes.

作者信息

Kawamoto Keisuke, Hayashi Yoshihito

机构信息

Department of Chemistry, Kanazawa University, Kanazawa, Japan.

出版信息

Front Chem. 2018 Aug 28;6:375. doi: 10.3389/fchem.2018.00375. eCollection 2018.

DOI:10.3389/fchem.2018.00375
PMID:30211155
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6121072/
Abstract

An isolation of a vanadium(V) oxide cluster mimicking VO layered structure was achieved formulated as [{Co(tacn)}VO(OH)] () (tacn = 1,4,7-triazacyclononane). From the V NMR spectra of the reaction mixtures, we optimized the reaction condition in terms of a molar ratio of VO and [Co(tacn)(HO)] as well as a pH value. Cluster is stable in a wide range of pH values from 1.5 to 8.0, and the presence of multiple hydrogen bondings in the structure is a unique feature. In the X-ray analysis of cluster , the V⋯ V distances are classified into two groups of relatively shorter distances (2.978(1) Å) and longer interactions (3.554(1) Å), and it is a good model of the substructure of VO bulk material. As far as we know, this is a first example of an isolation of mixed-metal cluster including a unit of VO structure by a stack of two layers of [HVO], although cubic VO cubane-type clusters are well known. The solid sample of compound and shows reversible thermochromic behavior accompanied by crystal to amorphous transformation upon hydration-dehydration process.

摘要

实现了一种模拟VO层状结构的五氧化二钒簇的分离，其化学式为[{Co(tacn)}VO(OH)]（ ）（tacn = 1,4,7-三氮杂环壬烷）。从反应混合物的钒核磁共振谱中，我们根据VO与[Co(tacn)(H₂O)]的摩尔比以及pH值优化了反应条件。簇合物 在1.5至8.0的广泛pH值范围内稳定，并且结构中存在多个氢键是其独特特征。在簇合物 的X射线分析中，V⋯V距离分为两组，相对较短的距离（2.978(1) Å）和较长的相互作用（3.554(1) Å），它是VO块状材料亚结构的良好模型。据我们所知，这是通过两层[HVO]堆叠分离出包含VO结构单元的混合金属簇的首个例子，尽管立方VO立方烷型簇是众所周知的。化合物 和 的固体样品在水合 - 脱水过程中表现出可逆的热致变色行为，并伴随着晶体到非晶态的转变。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/250f4b5b4ad5/fchem-06-00375-g0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/75af6a34cca7/fchem-06-00375-g0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/819b3226e4a1/fchem-06-00375-g0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/dd9cd6cb36c3/fchem-06-00375-g0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/b49fe5e2c651/fchem-06-00375-g0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/a26aa79f6307/fchem-06-00375-g0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/406f505a8e6c/fchem-06-00375-g0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/250f4b5b4ad5/fchem-06-00375-g0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/75af6a34cca7/fchem-06-00375-g0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/819b3226e4a1/fchem-06-00375-g0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/dd9cd6cb36c3/fchem-06-00375-g0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/b49fe5e2c651/fchem-06-00375-g0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/a26aa79f6307/fchem-06-00375-g0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/406f505a8e6c/fchem-06-00375-g0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8dc5/6121072/250f4b5b4ad5/fchem-06-00375-g0006.jpg

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