Substituent Modulation of Contorted Hexa‐ peri ‐benzocoronene‐Based Conjugated Metal–Organic Frameworks for High‐Performance Capacitor

Abstract Two‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) exhibiting graphite‐like van der Waals stacked layers have been recognized as a new type of crystalline conductive materials and have shown rapid progress in the last decade. However, the purposive design and modulation of their conductive properties and related application performance remains a challenge. Herein, we present a new type of 2D c‐MOFs with contorted conformation and substituent‐modulated structures for highperformance of the capacitor. Octahydroxy‐hexa‐ peri ‐benzocoronene (HBCOH) with a contorted graphene nanosheet core is designed and synthesized as the ligand. The F‐substituted 2D c‐MOF FHBCOH‐Cu demonstrates superior crystallinity and conductive properties exhibiting a record‐breaking specific capacitance of 943 F g −1 at a rate of 0.5 A g −1 . The improved crystallinity, enhanced conductivity, and pore environment control enabled by halogen substitution, combined with the contorted conformation synergistically accomplish high performance of 2D c‐MOFs as electrode materials in supercapacitors. This study introduces a novel molecular design strategy for the construction of 2D c‐MOFs‐based high‐performance energy storage materials.