In general, due to the lack of efficient specific molecular interactions, achieving host-guest molecular recognition inside large and neutral metal-organic cages (MOCs) is challenging. Preferential molecular recognition of aromatics using the internal binding sites of interlocked icosahedral (i. e., spherical) M12 L8 MOCs within poly-[n]-catenane (1) is reported. The guest absorption was monitored directly in the solid-state by consecutive single-crystal-to-single-crystal (SCSC) reactions in a gas-solid environment, in single-crystal X-ray diffraction (SC-XRD) experiments. The preferential guest uptake was corroborated by density functional theory (DFT) calculations by determining the host-guest interaction energy (Ehost-guest ) with a nitrobenzene (NB)≫p-xylene (p-xy)≫o-dichlorobenzene (o-DCB) trend (i. e., from 44 to 25 kcal mol-1 ), assessing the XRD outcomes. Combining SC-XRD, DFT and solid-state 13 C NMR, the exceptional stability of the M12 L8 cages, together with the guest exchange/release properties were rationalized by considering the presence of mechanical bonds (efficient π-π interactions) and by the pyridine's rotor-like behaviour (with 3 kcal mol-1 rotational energy barrier). The structure-function properties of M12 L8 makes 1 a potential candidate in the field of molecular sensors.
Keywords: DFT calculations; M12L8 cages; mechanical bonds; molecular recognition; rotors.
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