Assembling Hierarchical Cluster Solids with Atomic Precision
Hierarchical solids created from the binary assembly of cobalt chalcogenide and iron oxide molecular clusters are reported. Six different molecular clusters based on the octahedral Co6E8 (E = Se or Te) and the expanded cubane Fe8O4 units are used as superatomic building blocks to construct these crystals. The formation of the solid is driven by the transfer of charge between complementary electron-donating and electron-accepting clusters in solution that crystallize as binary ionic compounds. The hierarchical structures are investigated by single-crystal X-ray diffraction, providing atomic and superatomic resolution. We report two different superstructures: a superatomic relative of the CsCl lattice type and an unusual packing arrangement based on the double-hexagonal close-packed lattice. Within these superstructures, we demonstrate various compositions and orientations of the clusters.
crystals, redox reactions, charge transfer, lattices, cluster chemistry
Turkiewicz, Ari, Daniel W. Paley, Tiglet Besara, Giselle Elbaz, Andrew Pinkard, Theo Siegrist, and Xavier Roy. "Assembling hierarchical cluster solids with atomic precision." Journal of the American Chemical Society 136, no. 45 (2014): 15873-15876.
Journal of the American Chemical Society