Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues.
Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues.
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DOI：
10.1021/acscentsci.5b00247
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发表时间：
2015-08-26
影响因子：
18.2
通讯作者：
Dincă M
中科院分区：
文献类型：
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作者：
Brozek CK;Michaelis VK;Ong TC;Bellarosa L;López N;Griffin RG;Dincă M
多核固态核磁共振，质谱，第一性原理分子动力学模拟和其他补充证据表明，金属有机框架（MOF）中最具标志性的材料之一MOF-5中Zn 2+离子周围的配位环境并不严格。Zn 2+离子结合溶剂分子，从而增加它们的配位数，并动态地从框架本身解离。平均而言，每个簇中的一个离子具有至少一个配位的N，N-二甲基甲酰胺（DMF）分子，使得所合成的MOF-5的式被定义为Zn 4 O（BDC）3（DMF）x（x = 1-2）。理解MOF-5的动态行为导致用于合成亚稳态Zn 4-xCoxO（对苯二甲酸酯）3（x > 1）材料的合理的低温阳离子交换方法，迄今为止，这还不能通过典型的高温溶剂热途径获得。通常被视为刚性和静态的，在MOF-5中的金属中心被示出动态地与配位溶剂相互作用。有了这个洞察力，我们获得了前所未有的亚稳态Co取代的类似物。
Multinuclear solid-state nuclear magnetic resonance, mass spectrometry, first-principles molecular dynamics simulations, and other complementary evidence reveal that the coordination environment around the Zn2+ ions in MOF-5, one of the most iconic materials among metal–organic frameworks (MOFs), is not rigid. The Zn2+ ions bind solvent molecules, thereby increasing their coordination number, and dynamically dissociate from the framework itself. On average, one ion in each cluster has at least one coordinated N,N-dimethylformamide (DMF) molecule, such that the formula of as-synthesized MOF-5 is defined as Zn4O(BDC)3(DMF)x (x = 1–2). Understanding the dynamic behavior of MOF-5 leads to a rational low-temperature cation exchange approach for the synthesis of metastable Zn4–xCoxO(terephthalate)3 (x > 1) materials, which have not been accessible through typical high-temperature solvothermal routes thus far. Typically viewed as rigid and static, the metal centers in MOF-5 are shown to interact dynamically with coordinating solvent. With this insight, we accessed unprecedented metastable Co-substituted analogues.