Superatoms are stable, atomically-precise clusters of bound atoms that show collective properties mimicking traditional atoms. Unlike traditional atoms though, the electronic structure of superatoms can be tuned by the substitution or modification of core atoms and surface ligands. Assembly of these superatoms into larger materials has shown to provide tunability of the resulting material’s properties based on the constituent superatom composition and the method of assembly. In my talk, I will discuss the work my lab and I have conducted utilizing superatomic cobalt-selenide Chevrel-type M6E8L6 clusters with substitutable ligands to fuse them into larger materials. Previous work from our lab has detailed a wet-chemistry synthesis of Co6Se8 clusters with photolytically-substitutable carbonyl ligands (CO) that have been used to assemble a variety of materials from polymers to MOFs. I will discuss the substitution of a photolytically-generated carbene to form a reversibly-bridging carbene ligand, allowing greater synthetic access to the cobalt-selenide cluster core. I will detail how the newly exposed core can be fused with another cluster core to form an electronically-coupled dimer and discuss it’s properties. I will then detail our studies of the reactive carbene-ligated cluster intermediate and it’s use to expand the ligand substitution chemistry of the cobalt-selenide cluster and the fused dimer. Finally, I will discuss the development of new carbene intermediates towards forming extended materials consisting of electronically-coupled, fused superatoms.