An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation

Abstract

The flexibility and unexpected dynamic behavior of a third-generation metal-organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl-based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5-benzenetricarboxylate) layers, providing a 3D porous structure (1). A phase transition of the solid can be induced to generate a new, nonporous 2D structure (2) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single-crystal-to-single-crystal transformation by single-crystal and powder X-ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl₃ or supercritical CO₂ induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C₆₀ is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.