3D π–d Conjugated Coordination Polymer Enabling Ultralong Life Magnesium‐Ion Storage

Abstract There has been increasing interests in π–d conjugated coordination polymers (CCPs) for energy storage because of their rapid charge transfer through long‐range planar π–d conjugation between ligands and metal centers. Nevertheless, currently reported CCPs for energy storage are mostly based on 1D or 2D structures. There are few 3D CCPs reported to date because of the great challenge in constructing nonplanar coordination geometries, let alone their applications in multivalent ions storage. Herein, a triphenylene‐catecholate‐based 3D CCP (Mn‐HHTP) is successfully synthesized assembled from the multidentate chelating groups of hexahydroxytriphenylene (HHTP) ligands and their isotropic coordination with Mn²⁺ ions. The 3D conjugated structure of Mn‐HHTP enables an exceptional cycle life of >4000 cycles at 0.5 A g⁻¹ for multivalent Mg²⁺ ion storage, which is far superior to most organic and inorganic electrode materials. Experimental characterizations combined with theoretical calculations indicate that the semiquinone radicals at the HHTP ligands are the electroactive centers for Mg²⁺ ions storage. The excellent performance of Mn‐HHTP opens a new avenue towards the design of 3D CCPs for long‐life rechargeable magnesium‐ion batteries.