4 years ago

Ultrafast Molecular Rotors and Their CO2 Tuning in MOFs with Rod-Like Ligands

Ultrafast Molecular Rotors and Their CO2 Tuning in MOFs with Rod-Like Ligands
Angelo Maspero, Simona Galli, Mattia Negroni, Angiolina Comotti, Fabio Castiglioni, Piero Sozzani, Silvia Bracco
A metal organic framework (MOF) engineered to contain in its scaffold rod-like struts featuring ultrafast molecular rotors showed extremely rapid 180 ° flip reorientation with rotational rates of 1011 Hz at 150 K. Crystal-pore accessibility of the MOF allowed the CO2 molecules to enter the cavities and control the rotor spinning speed down to 105 Hz at 150 K. Rotor dynamics, as modulated by CO2 loading/unloading in the porous crystals, was described by proton T1 and 2H NMR spectroscopy. This strategy enabled the regulation of rotary motion by the diffusion of the gas within the channels and the determination of the energetics of rotary dynamics in the presence of CO2. MOF, I′m only dancing: CO2 gas flows into the Zn-based MOF which sustains ultrafast rotors and intervenes actively in the motional mechanics, increasing reversibly the energy barrier for rotation and allowing active manipulation of molecular rotor dynamics (see figure).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702930

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