Using mechanochemistry by grinding TPB and ZnBr2 an amorphous poly-[n]-catenane of interlocked M12L8 nanocages is obtained in good yields (⁓ 80 %) and within 15 minutes. The mechanical bond among...

Here, we show that in a supramolecular system with more than 20 building blocks forming large icosahedral M12L8 metal–organic cages (MOCs), using the instant synthesis method, it is possible to kinetically trap and control the formation of interlocking M12L8 nanocages, giving rare M12L8 TPB-ZnI2 poly-[n]-catenane. The catenanes are obtained in a one-pot reaction, selectively as amorphous (a1) or crystalline states, as demonstrated by powder X-ray diffraction (powder XRD), thermogravimetric (TG) analysis and 1H NMR. The 300 K M12L8 poly-[n]-catenane single crystal X-ray diffraction (SC-XRD) structure including nitrobenzene (1) indicates strong guest binding with the large M12L8 cage (i.e., internal volume ca. 2600 Å3), allowing its structural resolution. Conversely, slow self-assembly (5 days) leads to a mixture of the M12L8 poly-[n]-catenane and a new TPB-ZnI2 (2) coordination polymer (i.e., thermodynamic product), as revealed by SC-XRD. The neat grinding solid-state synthesis also yields amorphous M12L8 poly-[n]-catenane (a1′), but not coordination polymers, selectively in 15 min. The dynamic behavior of the M12L8 poly-[n]-catenanes demonstrated by the amorphous-to-crystalline transformation upon the uptake of ortho-, meta- and para-xylenes shows the potential of M12L8 poly-[n]-catenanes as functional materials in molecular separation. Finally, combining SC-XRD of 1 and DFT calculations specific for the solid-state, the role of the guests in the stability of the 1D chains of M12L8 nanocages is reported. Energy interactions such as interaction energies (E), lattice energies (E*), host–guest energies (Ehost-guest) and guest-guest energies (Eguest-guest) were analysed considering the X-ray structure with and without the nitrobenzene guest. Not only the synthetic control achieved in the synthesis of the M12L8 MOCs but also their dynamic behavior either in the crystalline or amorphous phase are sufficient to raise scientific interest in areas ranging from fundamental to applied sides of chemistry and material sciences.

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) M12L8MOCs within poly‐[n]‐catenane (1) is reported. The guest absorption has been monitored directly in the solid‐state by consecutive single‐crystal‐to‐single‐crystal (SCSC) reactions in a gas‐solid environment, using single‐crystal X‐ray diffraction (SC‐XRD) experiments. The preferential guest uptake is corroborated by Density Functional Theory (DFT) calculations by determining the host‐guest interaction energy (Ehost‐guest) with the nitrobenzene (NB) >> p‐xylene (p‐xy) >> o‐dichlorobenzene (o‐DCB) trend (i.e., from 44 kcal/mol to 25 kcal/mol), assessing the XRD outcomes. Combining SC‐XRD, DFT and solid‐state 13C NMR, the exceptional stability of the M12L8 cages, together with the guest exchange/release properties are rationalized by the presence of mechanical bonds (efficient π‐π interactions) and by the pyridine’s rotor‐like behaviour (with 3 kcal/mol rotational energy barrier). The structure‐function properties of M12L8 makes 1 a potential candidate in the field of molecular sensors.