Dynamic coordination bonding in metal–organic frameworks: fundamental concepts and emerging applications

Abstract

Metal–organic frameworks (MOFs) have long been regarded as rigid crystalline solids with static coordination bonds. Mounting spectroscopic and crystallographic evidence, however, shows that these bonds are dynamic, undergoing transient dissociation and reassociation without loss of framework integrity. This recognition has catalyzed the concept of dynamic coordination bonding, offering a fresh perspective on MOF chemistry and function. In this Review, we define this concept and organize it into two complementary modes: (i) metal–guest dynamics at open metal sites and (ii) metal–linker dynamics within the lattice. We combine experimental and theoretical evidence demonstrating that bond dynamics underpin key functions—including non-thermal activation, gas adsorption, heterogeneous catalysis, and the formation of liquid and glassy MOFs. By integrating mechanistic insight with application-level performance, we establish dynamic bonding as a central design principle for MOFs and outline practical levers—metal identity, linker electronics and sterics, pore architecture, and crystal dimension—to tune equilibrium populations. Framed in this way, MOFs emerge not as static scaffolds but as responsive coordination networks, enabling next-generation advances in catalysis, gas storage and separations, and energy-relevant processes.