Substituent modulation of contorted hexa‐peri‐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 shown rapid progress in the last decade. However, purposively design and modulation of their conductive properties and related application performance remains challenge. Herein, we present a new type of 2D c‐MOFs with contorted conformation and substituent‐modulated structures for high performance of 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 supercapacitor. This study introduces a novel molecular design strategy for the construction of 2D c‐MOFs‐based high‐performance energy storage materials.