Our understanding on the nature of weak intermolecular metal–metal interactions as well as of multiple bonding in group 15/16 chemistry, in particular of compounds containing the heaviest elements of both groups – Sb, Bi, Se, and Te – is still scarce. These types of interactions are particularly important for the chemical and physical properties of such main group element compounds. For instance, the formation and disruption of weak intermolecular metal–metal interactions are the origin of the so-called thermochroism. The structural characterization of compounds containing sterically less demanding organic substituents is therefore of particular interest, since the capability of small substituents to kinetically stabilize the respective metal centers – and hence to suppress intermolecular interactions – is expected to be rather less pronounced.

We will herein summarize the most recent results reported for the synthesis and structural characterization of group 15/16 compounds containing a direct (polar-covalent) element–element bond including compounds containing a terminal, formally double bond. In addition, the capability of selected compounds to serve as single-source precursor for the synthesis of the corresponding nanomaterials, in particular Sb₂Te₃ and Bi₂Te₃, by using wet chemical methods as well as gas phase approaches such as metal organic chemical vapor deposition (MOCVD) processes will be demonstrated.