Assembling Hierarchical Cluster Solids with Atomic Precision

Abstract

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.

Document Type

Article

DOI

https://doi.org/10.1021/ja508698w

Keywords

crystals, redox reactions, charge transfer, lattices, cluster chemistry

Publication Date

2014

Journal Title

Journal of the American Chemical Society

Link to Full Text

Share

COinS