Electrochemical Doping of Two-Dimensional Superatomic Materials.

We report an electrochemical method for doping two-dimensional (2D) superatomic semiconductor ReSeCl that significantly improves the material's electrical transport while retaining the in-plane and stacking structures. The electrochemical reduction induces the complete dissociation of chloride anions from the surface of each superatomic nanosheet. After the material is dehalogenated, we observe the electrical conductivity () increases by two orders of magnitude while the 3D electron carrier density () increases by three orders of magnitude.

Electron and Spin Delocalization in [Co Se (PEt ) ] Superatoms.

Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid-state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co Se (PEt ) . We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co Se ] core while ligands function as an insulated shell.

Functional Monolayers on a Superatomic Pegboard.

We advance the chemistry of apical chlorine substitution in the 2D superatomic semiconductor ReSeCl to build functional and atomically precise monolayers on the surface of the 2D superatomic ReSe substrate. We create a functional monolayer by installing surface (2,2'-bipyridine)-4-sulfide (Sbpy) groups that chelate to catalytically active metal complexes. Through this reaction chemistry, we can create monolayers where we can control the distribution of catalytic sites.

Site-Selective Surface Modification of 2D Superatomic ReSe.

Coating two-dimensional (2D) materials with molecules bearing tunable properties imparts their surfaces with functionalities for applications in sensing, nanoelectronics, nanofabrication, and electrochemistry. Here, we report a method for the site-selective surface functionalization of 2D superatomic ReSeCl monolayers. First, we activate bulk layered ReSeCl by intercalating lithium and then exfoliate the intercalation compound LiReSeCl in -methylformamide (NMF).

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.