Dipolar order in an amphidynamic crystalline metal–organic framework through reorienting linkers

Su, Yangyang; Lamb, Elinor; Liepuoniute, Ieva; Chronister, Aaron; Stanton, Annette L.; Guzmán, Pedro E. Encinosa; Pérez-Estrada, Salvador; Chang, T.; Houk, K. N.; Garcı́a-Garibay, Miguel A.; Brown, Stuart

doi:10.1038/s41557-020-00618-6

Cited by 32 publications

(33 citation statements)

References 24 publications

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“…Within the realm of porous materials, MOFs are outstanding for their synthetic versatility and the opportunity they provide to design modular structures, while preserving crystalline order and periodicity. , Moreover, MOFs have been shown to support extensive dynamics without disrupting the primary architecture. For this reason, MOFs were successfully employed to insert rotors in the frameworks as ligands bridging the metal ions or cluster nodes. − The project to assemble multiple fast rotors of increasing complexity within a single ordered framework is further challenging, since the framework not only preserves their peculiar mobility but enhances their synergistic potential for realizing a cooperative smart organization with emerging functions. Pillared-MOFs offer this opportunity being composed of two juxtaposed ligands, which can be designed as molecular rotors.…”

Section: Introductionmentioning

confidence: 99%

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO₂

et al. 2021

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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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Section: Introductionmentioning

confidence: 99%

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO₂

et al. 2021

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“…undergoes rotational (35)(36)(37)(38) or linear (39,40) movements of a nondirectional nature (35)(36)(37)(38)(39)(40)(41)(42). In one instance, Danowski et al (43) have described the unidirectional rotary motion of motors in a MOF.…”

Section: Active Mechanisorption Driven By Pumping Cassettesmentioning

confidence: 99%

Active mechanisorption driven by pumping cassettes

Feng

Qiu

Guo

et al. 2021

Science

119

116

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Pumping macrocycles onto surfaces Numerous chemical processes, ranging from water purification to catalysis, involve sorption of small molecules onto surfaces. Typically, spontaneous attractive interactions favor the binding event. Feng et al . report a mechanisorption process that requires redox manipulations to pump macrocycles from bulk solution onto axles immobilized on a metal-organic framework. The resulting rotaxanes store energy through nonequilibrium charge concentration in their mechanical bonds. Ultimately, the technique could also prove useful for actively partitioning compounds with particular functionality between surface and bulk environments. —JSY

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“…In particular, MOF molecular machines may attract particular attention. [95,96] Second, the use of stimuli such as electric/magnetic fields and light will provide a remote and quick process of transferring the energy to the framework for initiation of its structural/ electronic transformations. So far, such a fast process has been demonstrated using light (Figure 12), [37] but we expect magnetic and electrical switching at higher rates to be demonstrated in the near future as well.…”

Section: What's New?mentioning

confidence: 99%

MOF‐Based Sustainable Memory Devices

Kulachenkov

Haar

Шипиловских

et al. 2021

Adv Funct Materials

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Data storage, processing, and communications are the backbone of the digital world and focus the innovation efforts of the microelectronics industry. Recent raw material shortages, however, have revealed the danger of sourcing for the digital industry. At a time of a significant increase in demand for data storage systems, it is urgent to consider the sustainability of the resources used for devices. By diluting inorganic elements in an organic matrix, metal-organic frameworks (MOFs) are of substantial interest for sustainable technologies. Moreover, they have shown great potential as active materials for electronic, optical, and magnetic memory devices, paving the way to accessible, sustainable, and recyclable microelectronic devices. Based on the number of fundamental studies of the bistability of MOFs, their scalability, recyclability, and low energy consumption, MOFs are highlighted as sustainable materials for a new generation of memristive devices. Finally, considering the "green" chemistry of specific MOF, their flexibility, as well as the market of microelectronics and mineral consumption, the future development of MOF-based memory devices and socio-economic profits from their utilization is predicted.

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Dipolar order in an amphidynamic crystalline metal–organic framework through reorienting linkers

Cited by 32 publications

References 24 publications

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO₂

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO₂

Active mechanisorption driven by pumping cassettes

MOF‐Based Sustainable Memory Devices

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Dipolar order in an amphidynamic crystalline metal–organic framework through reorienting linkers

Cited by 32 publications

References 24 publications

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO2

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO2

Active mechanisorption driven by pumping cassettes

MOF‐Based Sustainable Memory Devices

Contact Info

Product

Resources

About

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO₂

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO₂