Molecular Recognition of Aromatics in Spherical Nanocages

Abstract 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) M 12 L 8 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 ( E host–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 M 12 L 8 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 M 12 L 8 makes 1 a potential candidate in the field of molecular sensors.