Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO(2).
Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO(2).
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DOI：
10.1021/jacs.1c03801
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发表时间：
2021-08-25
影响因子：
15
通讯作者：
Comotti A
中科院分区：
文献类型：
--
作者：
Perego J;Bezuidenhout CX;Bracco S;Prando G;Marchiò L;Negroni M;Carretta P;Sozzani P;Comotti A
实现齿轮分子转子与固体中可忽略不计的能量需求的复杂并置，可以实现快速、可控和相关的旋转运动，以构建开关和电机。我们的努力是实现在MOF架构中运行的多个转子，即使在极冷的温度下也能支持快速运动状态。两种不同的配体，4,4 ' -联吡啶（bipy）和双环[1.1.1]戊二羧酸酯（BCP），配位到锌簇上，形成了柱层三维正交转子阵列。温度为2k的变温XRD、2H固体回波和1H T1弛豫核磁共振揭示了BCP的超快迁移率和前所未有的由不同能量垒调制的级联机制，从100 J mol-1 （24 cal mol-1）开始，这是复杂转子阵列的真正基准。这些转子探索了转换和非旋转关系的多种配置，通过热能打开和关闭，这是DFT建模支持的场景。此外，双环的集体旋转与框架协调一致，在动力结构中在两种排列之间进行可控摆动。第二种通过外部刺激操纵转子的方法是使用二氧化碳，二氧化碳通过开放的孔隙扩散，极大地改变了全球旋转机制。总的来说，多个转子的有趣运动，协同设计并集成到同一个框架中，为在类似机器的双配体MOF晶体中设计超移动转子（4k时107 Hz）提供了机会。
Achieving sophisticated juxtaposition of geared molecular rotors with negligible energy-requirements in solids enables fast yet controllable and correlated rotary motion to construct switches and motors. Our endeavor was to realize multiple rotors operating in a MOF architecture capable of supporting fast motional regimes, even at extremely cold temperatures. Two distinct ligands, 4,4′-bipyridine (bipy) and bicyclo[1.1.1]pentanedicarboxylate (BCP), coordinated to Zn clusters fabricated a pillar-and-layer 3D array of orthogonal rotors. Variable temperature XRD, 2H solid-echo, and 1H T1 relaxation NMR, collected down to a temperature of 2 K revealed the hyperfast mobility of BCP and an unprecedented cascade mechanism modulated by distinct energy barriers starting from values as low as 100 J mol–1 (24 cal mol–1), a real benchmark for complex arrays of rotors. These rotors explored multiple configurations of conrotary and disrotary relationships, switched on and off by thermal energy, a scenario supported by DFT modeling. Furthermore, the collective bipy-ring rotation was concerted with the framework, which underwent controllable swinging between two arrangements in a dynamical structure. A second way to manipulate rotors by external stimuli was the use of CO2, which diffused through the open pores, dramatically changing the global rotation mechanism. Collectively, the intriguing gymnastics of multiple rotors, devised cooperatively and integrated into the same framework, gave the opportunity to engineer hypermobile rotors (107 Hz at 4 K) in machine-like double ligand MOF crystals.
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影响因子：
4.9
作者：
Bajpai, Alankriti;Lusi, Matteo;Zaworotko, Michael J.
通讯作者：
Zaworotko, Michael J.
影响因子：
16.6
作者：
Bracco, Silvia;Beretta, Mario;Sozzani, Piero
通讯作者：
Sozzani, Piero
DOI：
10.1039/ft9949003023
发表时间：
1994-10-21
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
影响因子：
--
作者：
HENSEL, KD;GERRY, MCL
通讯作者：
GERRY, MCL
影响因子：
16.6
作者：
Horike, Satoshi;Matsuda, Ryotaro;Kitagawa, Susumu
通讯作者：
Kitagawa, Susumu
影响因子：
38.3
作者：
Danowski, Wojciech;van Leeuwen, Thomas;Feringa, Ben L.
通讯作者：
Feringa, Ben L.