Controlling Ligand Coordination Spheres and Cluster Fusion in Superatoms.

We show that reaction pathways from a single superatom motif can be controlled through subtle electronic modification of the outer ligand spheres. Chevrel-type [CoSeL] (L = PR, CO) superatoms are used to form carbene-terminated clusters, the reactivity of which can be influenced through the electronic effects of the surrounding ligands. This carbene provides new routes for ligand substitution chemistry, which is used to selectively install cyanide or pyridine ligands which were previously inaccessible in these cobalt-based clusters.

Electron Cartography in Clusters.

Deconvoluting the atom-specific electron density within polynuclear systems remains a challenge. A multiple-wavelength anomalous diffraction study on four clusters that share the same [Co Se ] core was performed. Two cluster types were designed, one having a symmetric ligand sphere and the other having an asymmetric ligand sphere.

Superatom Fusion and the Nature of Quantum Confinement.

Quantum confinement endows colloidal semiconducting nanoparticles with many fascinating and useful properties, yet a critical limitation has been the lack of atomic precision in their size and shape. We demonstrate the emergence of quantum confined behavior for the first time in atomically defined CoSe(PEt) superatoms by dimerizing [CoSe] units through direct fusion. To accomplish this dimerization, we install a reactive carbene on the [CoSe] core to create a latent fusion site.

Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials.

The programmed assembly of nanoscale building blocks into multicomponent hierarchical structures is a powerful strategy for the bottom-up construction of functional materials. To develop this concept, our team has explored the use of molecular clusters as superatomic building blocks to fabricate new classes of materials. The library of molecular clusters is rich with exciting properties, including diverse functionalization, redox activity, and magnetic ordering, so the resulting cluster-assembled solids, which we term superatomic crystals (SACs), hold the promise of high tunability, atomic precision, and robust architectures among a diverse range of other material properties.

Two-Dimensional Nanosheets from Redox-Active Superatoms.

We describe a new approach to synthesize two-dimensional (2D) nanosheets from the bottom-up. We functionalize redox-active superatoms with groups that can direct their assembly into multidimensional solids. We synthesized CoSe[PEt(4-CHCOOH)] and found that it forms a crystalline assembly.

Weaving Nanoscale Cloth through Electrostatic Templating.

Here we disclose a simple route to nanoscopic 2D woven structures reminiscent of the methods used to produce macroscopic textiles. We find that the same principles used in macroscopic weaving can be applied on the nanoscale to create two-dimensional molecular cloth from polymeric strands, a molecular thread. The molecular thread is composed of CoSe(PEt)L superatoms that are bridged with L = benzene bis-1,4-isonitrile to form polymer strands.

Building Diatomic and Triatomic Superatom Molecules.

In this study, we have developed a method to create Co6Se8 superatoms in which we program the metal-ligand bonds. We exclusively form the Co6Se8 core under simple reaction conditions with a facile separation of products that contain differential substitution of the core. The combination of Co2(CO)8 and PR3 with excess Se gives the differentially and directionally substituted superatoms, Co6Se8(CO)x(PR3)(6-x).