Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal-Organic Chalcogenolate Assemblies

Herein, we report the use of sterically invariant carborane-based chalcogenols, containing exopolyhedral B-Se or B-S bonds, as ligands for the formation of photoluminescent copper(I)-based metal-organic chalcogenolate assemblies (MOCHAs). We show that precise tuning of the carborane dipole by changing the carborane isomer from meta- to ortho- allows for control over the MOCHA morphology and regulation of the resulting photophysical properties. Furthermore, microcrystal electron diffraction (MicroED) has been demonstrated as a powerful tool for metal chalcogenide structure elucidation. Through the use of MicroED, one of the isolated materials is determined to consist of zero-dimensional Cu4(Se-C2B10H11)4 clusters with an unprecedented Cu4Se4 geometry.