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

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.