Emergence of Coupled Rotor Dynamics in Metal-Organic Frameworks via Tuned Steric Interactions
Adrian Gonzalez-Nelson (Dutch Polymer Institute, TU Delft - Applied Sciences)
Srinidhi Mula (TU Delft - Applied Sciences)
Mantas Šimėnas (Vilnius University Institute of Biotechnology)
Sergejus Balčiū Nas (Vilnius University Institute of Biotechnology)
Adam R. Altenhof (National High Magnetic Field Laboratory, Florida State University)
Cameron S. Vojvodin (National High Magnetic Field Laboratory, Florida State University)
Stefano Canossa (Universiteit Antwerpen)
Jū Ras Banys (Vilnius University Institute of Biotechnology)
Monique A. Van Der Veen (TU Delft - Applied Sciences)
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Abstract
The organic components in metal-organic frameworks (MOFs) are unique: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. To fully exploit linker rotation, such as in the form of molecular machines, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows researchers to tune the rotors' steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of coupled rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gear-like cooperative motion in MOFs.
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