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 (E =17 cal mol ). H T 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: CO 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.
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