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.

Distinct properties of the triplet pair state from singlet fission

“…To establish the distinct chemical properties of the 1 (TT) state, we use the redox-active molecular cluster Fe 8 O 4 pz 12 Cl 4 (pz, pyrazolate), which we label [Fe 8 O 4 ], as an electron acceptor ( 48 , 49 ) and tether BP0 to [Fe 8 O 4 ] through a Fe-phenoxide bond (schematically illustrated in Fig. 1A).…”

A Filled‐Honeycomb‐Structured Crystal Formed by Self‐Assembly of a Janus Polyoxometalate–Silsesquioxane (POM–POSS) Co‐Cluster

“…[16] Most clusters can crystallize,but cannot form cocrystals with other clusters mainly because of differences in their structures and properties. [17][18][19] This situation means that it is difficult to guide incompatible clusters to form predesigned structures with desired performance,thus the development of CAMs is greatly limited. To overcome these difficulties,J anus particles [20][21][22] and co-clusters [23,24] have been devised with ad esire to boost the development of novel CAMs with expected properties and diverse structures.…”

The Artificial Bee Colony Algorithm for Global Optimization of Nanosized Clusters

“…Clusters can be assembled to build functional materials. 90 For example, since the electron-rich Co 6 Te 8 (PEt 3 ) 6 can reversibly donate up to 5 electrons 91 and fullerene C 60 acts as an electron acceptor, they are believed to be able to combine to give interesting materials. Indeed, solids of similar composition, Due to the large size of this system (~3.1 nm or 1000 atoms), local optimizations were only performed with xTB.…”