Porous Supramolecular Crystalline Probe that Detects Non‐Covalent Interactions Involved in Molecular Recognition of Furanic Compounds

Abstract Selective separation and conversion of furan‐based biomass‐derived compounds, which are closely related to biorefineries, is currently an important issue. To improve their performance, it is important to deepen the understanding of non‐covalent interactions that act on the molecular recognition of furanic compounds on separation or catalyst matrices. Here, a new method is reported to comprehensively visualize such intermolecular interactions using a porous supramolecular crystalline probe with polar and non‐polar binding sites within a low‐symmetric nanochannel consisting of four isomeric Pd ^II ₃ ‐macrocycles. Single‐crystal X‐ray diffraction analysis of the crystals including 5‐hydroxymethylfurfural, furfural, furfuryl alcohol, or 2‐acetylfuran reveals a variety of interactions involving their furan rings and polar substituents. It is also found that cooperative and competitive effects between guest and solvent molecules significantly change their recognition mode.