Solid State Machinery of Multiple Dynamic Elements in a Metal–Organic Framework

• DOI: 10.1002/ange.202317094
• Publication Date: 2024-01-18T16:45:43Z
• Authors: Jacopo Perego; Andrea Daolio; Charl X. Bezuiden...; Sergio Piva; Giacomo Prando; Benjamin Costarella; Pietro Carretta; Luciano Marchiò; Dominik Kubicki; Piero Sozzani; Silvia Bracco; Angiolina Comotti
• Keywords: Crystal Engineering, Metal-Organic Frameworks, Molecular Dynamics, Molecular Rotor, Solid State NMR;; Crystal Engineering; Settore CHEM-03/A - Chimica generale e inorganica; Molecular Rotor; Molecular Dynamic; 500; Settore CHEM-05/A - Chimica organica; 540; Solid State NMR; Metal-Organic Framework; Crystal Engineering; Metal-Organic Frameworks; Molecular Dynamics; Molecular Rotor; Solid State NMR

Abstract Engineering coordinated rotational motion in porous architectures enables the fabrication of molecular machines solids. A flexible two‐fold interpenetrated pillared Metal‐Organic Framework precisely organizes fast mobile elements such as bicyclopentane (BCP) (10 7 Hz regime at 85 K), two distinct pyridyl rotors and E ‐azo group involved pedal‐like motion. Reciprocal sliding sub‐networks, switched by chemical stimuli, modulated sizes channels finally overall dynamical machinery. Actually, iodine‐vapor adsorption drives a dramatic structural rearrangement, displacing subnets concerted piston‐like Unconventionally, BCP mobility increases, exploring ultra‐fast dynamics Hz) temperatures low 44 K, while diverge into faster slower symmetry lowering. Indeed, one pillar ring gained greater rotary freedom carried azo‐group crank‐like peculiar behavior was stimulated pressurized CO 2, which regulates upon incremental site occupation. The is intrinsically coupled to framework flexibility demonstrated complementary experimental evidence (multinuclear solid‐state NMR down very temperatures, synchrotron radiation XRD, gas sorption) computational modelling, helps elucidate highly sophisticated rotor‐structure interplay.