As atomically precise nanoscale clusters, superatoms represent an attractive class of building blocks for the design and synthesis of novel materials in two and three dimensions. Using the convenient cluster starting material trans-Co6Se8(CO)2(PPh3)4, we have synthesized an ideal, planar, four-way linker for cyanometalate coordination polymers: [trans-Co6Se8(CO)2(CN)4]n- (n=2-4). This equatorially cyanide-ligated cluster can be isolated in three oxidation states, including the air and water-stable di and trianions, and can be combined with transition metal salts to form coordination polymers. Additionally, the trans carbonyl positions of the cluster can be facilely replaced with functionalized isocyanides or phosphines, further diversifying the possible materials properties achievable using this synthetic building block. The synthesis, structure, and magnetism of the resulting family of 2 and 3-D materials will be presented, along with the exfoliation of the 2D materials to few-layer samples and characterization thereof.

From superatoms to materials: Synthesis of diverse cyanometalate coordination polymers from a single cluster building block

ACS Fall 2021

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