Advancing Electronic Application of Coordination Solids: Enhancing Electron Transport and Device Integration via Surface‐Mounted MOFs (SURMOFs)

Abstract The layer‐by‐layer (LbL) assembly of coordination solids, enabled by the surface‐mounted metal–organic framework (SURMOF) platform, yields thin films with well‐defined orientation, tunable thickness, low density of defects, and editable crystalline heteroepitaxy. Such high‐quality thin films are suited for integrating metal‐organic framework (MOF) materials into devices used in electronics and optoelectronics technologies. However, the potential of the SURMOF platform has not been fully realized due to its instability, poor electronic interaction/transport, and limited intercalation/heteroepitaxy functions. Leveraging the longstanding efforts in processing and functionalizing coordination networks, four directions are highlighted for fully unleashing the technological potential of the SURMOF platform: 1) cascade cyclization to form polycyclic aromatic, nanographene‐like scaffolds with strong electron polarizability and electroactivity; 2) crosslinking by fused‐aromatic and metal–thiolate bridges for improved charge transport and structural stability; 3) covalent‐ionic heteroepitaxy of conductive metal–thiolate layers alternating with metal‐aqua‐hydroxide layers to emulate the transport layer and the charge storage layer in high‐temperature superconductors of cuprates and iron pnictides; and 4) machine learning (ML)‐based methods to optimize synthesis conditions.