Computational evaluation of metal pentazolate frameworks: inorganic analogues of azolate metal-organic frameworks.
Computational evaluation of metal pentazolate frameworks: inorganic analogues of azolate metal-organic frameworks.
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DOI：
10.1039/c7sc05020h
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发表时间：
2018-04-07
期刊：
影响因子：
8.4
通讯作者：
Friščić T
中科院分区：
文献类型：
--
作者：
Arhangelskis M;Katsenis AD;Morris AJ;Friščić T
我们报告了对假设框架的周期性密度泛函理论评估，包括基于五氮酸盐离子的拓扑新颖的arhangelskite （arh）结构，五氮酸盐是芳香5元环阴离子系列中最终的全氮无机成员。五氮酸盐是氮酸盐系列芳香5元环阴离子中最终的全氮无机成员。作为一种偶氮酸盐配体，它具有与金属离子形成开放框架结构的潜力，这将是由其同系物形成的偶氮酸盐金属有机框架的无机类似物。然而，尽管五唑酸盐离子的低稳定性和难以捉摸的性质迄今为止阻碍了这种框架的合成，但计算研究只关注五唑酸盐作为一种配体，可以形成离散的茂金属结构。受最近首次分离和结构表征的鼓舞，在环境条件下稳定的五氮酸盐和金属配合物，我们现在探索五氮酸盐作为框架形成配体的作用。我们报告了一种计算周期密度-功能理论对假定的金属五唑盐框架的能量学和拓扑偏好的评估，这也揭示了一种拓扑新颖的框架结构。
We report a periodic density-functional theory evaluation of putative frameworks, including a topologically novel arhangelskite (arh) structure, based on the pentazolate ion, the ultimate all-nitrogen, inorganic member of the azolate series of aromatic 5-membered ring anions. Pentazolate is the ultimate all-nitrogen, inorganic member of the azolate series of aromatic 5-membered ring anions. As an azolate ligand, it has the potential to form open framework structures with metal ions, that would be inorganic analogues of azolate metal–organic frameworks formed by its congeners. However, while the low stability and elusive nature of the pentazolate ion have so far prevented the synthesis of such frameworks, computational studies have focused on pentazolate exclusively as a ligand that would form discrete metallocene structures. Encouraged by the recent first isolation and structural characterization of pentazolate salts and metal complexes stable at ambient conditions, we now explore the role of pentazolate as a framework-forming ligand. We report a computational periodic density-functional theory evaluation of the energetics and topological preferences of putative metal pentazolate frameworks, which also revealed a topologically novel framework structure.