Translational dynamics of a non-degenerate molecular shuttle imbedded in a zirconium metal–organic framework

Wilson, Benjamin H.; Abdulla, Louae M.; Schurko, Robert W.

doi:10.1039/d0sc06837c

Cited by 26 publications

(10 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the current study, we focused on the shuttling rate due to the embedding in the MOF. The small differences (underestimations) with respect to the measured data might thus be due to the absence of a solvation environment in the atomistic simulations, which is in line with experimental observations (63).…”

Section: Dynamics Of the Embedded Mbrssupporting

confidence: 85%

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

Kolodzeiski

Amirjalayer

2022

Sci. Adv.

View full text Add to dashboard Cite

Molecular machines enable external control of structural and dynamic phenomena at the atomic level. To efficiently transfer their tunable properties into designated functionalities, a detailed understanding of the impact of molecular embedding is needed. In particular, a comprehensive insight is fundamental to design hierarchical multifunctional systems that are inspired by biological cells. Here, we applied an on-the-fly trained force field to perform atomistic simulations of a systematically modified rotaxane functionalized metal-organic framework. Our atomistic studies reveal a symmetric and asymmetric interplay of the mechanically bonded rings (MBRs) within the framework depending on the local environment. As a result, their translational motion is modulated ranging from fast oscillatory behavior to cooperative and potentially directed shuttling. The derived picture of competitive interactions, which influence the operation mechanism of the MBRs embedded in these soft porous materials, promotes the development of responsive functional materials, which is a key step toward intelligent matter.

show abstract

Section: Dynamics Of the Embedded Mbrssupporting

confidence: 85%

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

Kolodzeiski

Amirjalayer

2022

Sci. Adv.

View full text Add to dashboard Cite

show abstract

“…The mechanics of motion in solids has been attracting increasing interest from the perspective of designing organized molecular rotors, motors, and machines, the goal being to control their functions and properties, such as the commutation of light into mechanical work, dielectric and optical properties, and ferroelectricity. − Different strategies have been addressed for the targeted construction of dynamic materials, including the use of self-assembly principles, host–guest compounds, and hybrid materials. − …”

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

View full text Add to dashboard Cite

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.

show abstract

“…By incorporating a non-degenerate molecular shuttle as an organic linker, the same research group reported the preparation of zirconium-based MOF UWDM-11. 148 The bistable molecular shuttle is constituted by a thread having two different benzimidazole stations, one functionalized with two bromine atoms and another with two pendant phenyl-carboxylate moieties, encircled by a [24]crown-8 cyclic component. The X-ray single-crystal structure of the interlocked ligand shows that the wheel preferentially surrounds the station attached to the phenyl dicarboxylate groups (Fig.…”

Section: Ph-and Solvent-responsive Morfsmentioning

confidence: 99%

Mechanically interlocked molecules in metal–organic frameworks

et al. 2022

View full text Add to dashboard Cite

show abstract

Translational dynamics of a non-degenerate molecular shuttle imbedded in a zirconium metal–organic framework

Abstract: An unsymmetrical molecular shuttle was incorporated into the octahedral cavities of a Zr(iv) MOF. 13C SSNMR showed that the presence of mesitylene in the pores results in an increase in the barriers for the thermally driven motion of the macrocycle.

Cited by 26 publications

References 45 publications

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

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

Mechanically interlocked molecules in metal–organic frameworks

Contact Info

Product

Resources

About

Translational dynamics of a non-degenerate molecular shuttle imbedded in a zirconium metal–organic framework

Abstract: An unsymmetrical molecular shuttle was incorporated into the octahedral cavities of a Zr(iv) MOF. 13C SSNMR showed that the presence of mesitylene in the pores results in an increase in the barriers for the thermally driven motion of the macrocycle.

Cited by 26 publications

References 45 publications

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

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

Mechanically interlocked molecules in metal–organic frameworks

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