Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

Abstract

Abstract Functional materials that respond to chemical or physical stimuli through reversible structural transformations are highly desirable for the integration into devices. Now, a new stable and flexible eightfold interpenetrated three‐dimensional (3D) metal–organic framework (MOF) is reported, [Zn(oba)(pip)] n (JUK‐8) based on 4,4′‐oxybis(benzenedicarboxylate) (oba) and 4‐pyridyl functionalized benzene‐1,3‐dicarbohydrazide (pip) linkers, featuring distinct switchability in response to guest molecules (H 2 O and CO 2 ) or temperature. Single‐crystal X‐ray diffraction (SC‐XRD), combined with density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations, reveal a unique breathing mechanism involving collective motions of eight mixed‐linker diamondoid subnetworks with only minor displacements between them. The pronounced stepwise volume change of JUK‐8 during water adsorption is used to construct an electron conducting composite film for resistive humidity sensing.