Aligning Chemical Kinetics with Crystallization Enables Millimeter-Scale Single Crystals of Conductive MOFs

Conductive metal-organic frameworks (c-MOFs) are promising functional materials, yet their atomic-level clarity remains obscured by the limited size of available single crystals (typically <10 μm). We demonstrate that the kinetic mismatch between redox-coordination processes and crystal growth is the underlying obstacle, and propose a general strategy to reduce this mismatch by balancing the ligand acid-base equilibrium to control the redox-coordination kinetics. This kinetic aligning strategy enables the growth of single crystals up to over 1 mm in seven c-MOFs, and reveals three new crystal structures with distinct electronic properties. Single-crystal devices demonstrate record-high intrinsic electron-proton dual conductivity among porous MOFs. This work establishes both a fundamental framework and a practical strategy for growing c-MOF single crystals and designing materials that integrate electronic and protonic transport.