Synthetic Routes for a 2D Semiconductive Copper Hexahydroxybenzene Metal–Organic Framework

Conductive metal–organic frameworks (c-MOFs) have shown outstanding performance in energy storage and electrocatalysis. Varying the bridging metal species and the coordinating atom are versatile approaches to tune their intrinsic electronic properties in c-MOFs. Herein we report the first synthesis of the oxygen analog of M3(C6X6)2 (X = NH, S) family using Cu(II) and hexahydroxybenzene (HHB), namely Cu-HHB [Cu3(C6O6)2], through a kinetically controlled approach with a competing coordination reagent. We also successfully demonstrate an economical synthetic approach using tetrahydroxyquinone as the starting material. Cu-HHB was found to have a partially eclipsed packing between adjacent 2D layers and a bandgap of approximately 1 eV. The addition of Cu-HHB to the family of synthetically realized M3(C6X6)2 c-MOFs will enable greater understanding of the influence of the organic linkers and metals, and further broadens the range of applications for these materials.