Solvent and Steric Influences on Rotational Dynamics in Porphyrinic Metal–Organic Frameworks with Mechanically Interlocked Pillars,Crystal Growth & Design

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Solvent and Steric Influences on Rotational Dynamics in Porphyrinic Metal–Organic Frameworks with Mechanically Interlocked Pillars
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2019-08-28 , DOI: 10.1021/acs.cgd.9b00669
Pablo Martinez-Bulit ₁ , Christopher A. O’Keefe ₁ , Kelong Zhu ₁ , Robert W. Schurko ₁ , Stephen J. Loeb ₁

Affiliation

Zinc(II) metal–organic framework (MOF) materials were prepared using a porphyrin-based tetracarboxylate linker and pyridine-terminated [2]rotaxane linkers as pillars. Two pillaring rotaxanes (R = H or CH₃ at pyridine 2-position) were used to create two MOFs α-UWDM-6 and α-UWDM-7, and their structures were determined by single-crystal X-ray diffraction. Both MOFs undergo reversible phase transitions upon solvent removal to generate γ-UWDM-6 and β-UWDM-7. The dynamics of the 24-membered macrocycle ([24]crown-6) inside each MOF phase was studied using variable-temperature ²H solid-state NMR spectroscopy. Interestingly, only solvated α-UWDM-7 demonstrates unrestricted rotation of the macrocycle inside the MOF pores; studies on α-UWDM-7 with various solvents showed that the dynamics of the wheel is essentially independent of the solvent.

中文翻译：

机械联锁的卟啉金属-有机骨架中溶剂和金属对旋转动力学的影响

锌（II）金属-有机骨架（MOF）材料是使用基于卟啉的四羧酸酯连接基和吡啶末端的[2]轮烷连接基制备的。使用两个柱状轮烷（在吡啶2位的R = H或CH ₃）生成两个MOFα-UWDM-6和α-UWDM-7，并通过单晶X射线衍射确定其结构。两种MOF在去除溶剂后均经历可逆相变，生成γ-UWDM-6和β-UWDM-7。使用可变温度² H固态NMR光谱研究了每个MOF相内部的24元大环（[24] cro-6）的动力学。有趣的是，只有溶剂化的α-UWDM-7证明MOF孔内大环的旋转不受限制；用各种溶剂对α-UWDM-7进行的研究表明，砂轮的动力学特性基本上与溶剂无关。

更新日期：2019-08-29

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