Conjugated coordination polymers (CCPs), which possesslong-rangeplanar pi-d conjugation, are fascinating for various applicationsbecause they inherit the merits of both metal-organic frameworks(MOFs) and conducting polymers. However, only one-dimensional (1D)and two-dimensional (2D) CCPs have been reported so far. The synthesisof three-dimensional (3D) CCPs is challenging and even seems theoreticallyinfeasible because conjugation implies 1D or 2D structure. Besides,the redox activity of the conjugated ligands and the pi-dconjugation makes the synthesis of CCPs very complicated, and hence,single crystals of CCPs are rarely achieved. Herein, we reported thefirst 3D CCP and its single crystals with atomically precise structures.The synthesis process involves complicated in situ dimerization, deprotonationof ligands, oxidation/reduction of both ligands and metal ions, andprecise coordination between them. The crystals contain in-plane 1D pi-d conjugated chains and close pi-pi interactions between the adjacent chains that are bridged by anothercolumn of stacked chains, thus forming 3D CCP with high conductivity(400 S m(-1) at room temperature and 3100 S m(-1) at 423 K) and potential applications as cathodesin sodium-ion batteries with high capacity, rate capability, and cyclability.
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