Exploring the dynamics of Zr-based metal–organic frameworks containing mechanically interlocked molecular shuttles,Faraday Discussions

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Exploring the dynamics of Zr-based metal–organic frameworks containing mechanically interlocked molecular shuttles
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-4-16 , DOI: 10.1039/d0fd00004c
Ghazale Gholami ₁ , Benjamin H Wilson , Kelong Zhu , Christopher A O'Keefe , Robert W Schurko , Stephen J Loeb

Affiliation

Zr(IV) metal–organic frameworks (MOFs) UiO-68 and PCN-57, containing triphenylene dicarboxylate (TPDC) and tetramethyl-triphenylene dicarboxylate (TTDC) linkers, respectively, were doped with an H-shaped tetracarboxylate linker that contains a [2]rotaxane molecular shuttle. The new MOFs, UWDM-8 and UWDM-9, contain a [2]rotaxane crossbar spanning the tetrahedral cavities of the fcu topology while the octahedral cavities remain empty. ¹³C solid-state NMR (SSNMR) spectra and solution ¹H NMR spectra verified that the [2]rotaxanes were included as designed. Variable-temperature (VT) cross polarization (CP) magic-angle spinning (MAS) ¹³C SSNMR was used to explore the translational motion of the macrocyclic ring in both MOFs. The SSNMR results clearly show that the structure of the linker (TPDCvs.TTDC) affects the shuttling rate of the macrocyclic ring, although questions remain as to how rotation of the central phenylene unit of the strut might also affect the motion of the macrocycle.

中文翻译：

探索含机械互锁分子梭的Zr基金属有机骨架的动力学

Zr（IV）金属有机骨架（MOF）UiO-68和PCN-57分别包含三苯二甲酸二羧酸酯（TPDC）和四甲基三苯二甲酸二甲酯（TTDC）接头，并掺杂有H型四羧酸酯接头，该接头含有[ 2]轮烷分子穿梭。新的MOF UWDM-8和UWDM-9包含[2]轮烷交叉开关，跨越fcu拓扑的四面体腔，而八面体腔保持空白。¹³ C固态NMR（SSNMR）光谱和溶液¹1 H NMR光谱证实，[2]轮烷类被包括在内。可变温度（VT）交叉极化（CP）幻角旋转（MAS）¹³ C SSNMR用于研究两个MOF中大环的平移运动。SSNMR结果清楚地表明，连接子的结构（TPDC与TTDC）会影响大环的穿梭速率，尽管仍然存在有关支杆中央亚苯基单元的旋转如何也会影响大环运动的问题。

更新日期：2020-04-16

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