Herein, a novel D4 symmetrical redox‐active ligand tetrathia[8]circulene‐2,3,5,6,8,9,11,12‐octaol (8OH‐TTC) is designed and synthesized, which coordinates with Ni2+ ions to construct a 2D conductive metal‐organic framework (2D c‐MOF) named Ni‐TTC. Ni‐TTC exhibits typical semiconducting properties with electrical conductivity up to ≈1.0 S m−1 at 298 K. Furthermore, magnetism measurements show the paramagnetic property of Ni‐TTC with strong antiferromagnetic coupling due to the presence of semiquinone ligand radicals and Ni2+ sites. In virtue of its decent electrical conductivity and good redox activity, the gravimetric capacitance of Ni‐TTC is up to 249 F g−1 at a discharge rate of 0.2 A g−1, which demonstrates the potential of tetrathia[8]circulene‐based redox‐active 2D c‐MOFs in energy storage applications.
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