Fluorinated Metal-Organic Frameworks (MOFs), comprising a wheel-shaped ligand with geminal rotating fluorine atoms, produced benchmark mobility of correlated dipolar rotors at 2 K, with practically null activation energy (Ea=17 cal mol−1). 1H T1 NMR revealed multiple relaxation phenomena due to the exchange among correlated dipole-rotor configurations. Synchrotron radiation X-ray diffraction at 4 K, Density Functional Theory, Molecular Dynamics and phonon calculations showed the fluid landscape and pointed out a cascade mechanism converting dipole configurations into each other. Gas accessibility, shown by hyperpolarized-Xe NMR, allowed for chemical stimuli intervention: CO2 triggered dipole reorientation, reducing their collective dynamics and stimulating a dipole configuration change in the crystal. Dynamic materials under limited thermal noise and high responsiveness enable the fabrication of molecular machines with low energy dissipation and controllable dynamics.

Perego, J., Bezuidenhout, C., Bracco, S., Piva, S., Prando, G., Aloisi, C., et al. (2023). Benchmark Dynamics of Dipolar Molecular Rotors in Fluorinated Metal-Organic Frameworks. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, 62(5), 1-8 [10.1002/anie.202215893].

Benchmark Dynamics of Dipolar Molecular Rotors in Fluorinated Metal-Organic Frameworks

Perego, J
Co-primo
;
Bezuidenhout, C
Co-primo
;
Bracco, S
;
Piva, S;Sozzani, P;Daolio, A;Comotti, A
2023

Abstract

Fluorinated Metal-Organic Frameworks (MOFs), comprising a wheel-shaped ligand with geminal rotating fluorine atoms, produced benchmark mobility of correlated dipolar rotors at 2 K, with practically null activation energy (Ea=17 cal mol−1). 1H T1 NMR revealed multiple relaxation phenomena due to the exchange among correlated dipole-rotor configurations. Synchrotron radiation X-ray diffraction at 4 K, Density Functional Theory, Molecular Dynamics and phonon calculations showed the fluid landscape and pointed out a cascade mechanism converting dipole configurations into each other. Gas accessibility, shown by hyperpolarized-Xe NMR, allowed for chemical stimuli intervention: CO2 triggered dipole reorientation, reducing their collective dynamics and stimulating a dipole configuration change in the crystal. Dynamic materials under limited thermal noise and high responsiveness enable the fabrication of molecular machines with low energy dissipation and controllable dynamics.
Articolo in rivista - Articolo scientifico
Crystal Engineering; Fluorine; Metal Organic Frameworks; Molecular Dynamics; Molecular Rotor;
English
5-dic-2022
2023
62
5
1
8
e202215893
partially_open
Perego, J., Bezuidenhout, C., Bracco, S., Piva, S., Prando, G., Aloisi, C., et al. (2023). Benchmark Dynamics of Dipolar Molecular Rotors in Fluorinated Metal-Organic Frameworks. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, 62(5), 1-8 [10.1002/anie.202215893].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/430058
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