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 (MO-CHAs). 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 Cu-4(Se-C2B10H11)(4) clusters with an unprecedented Cu4Se4 geometry.

Automated summary

In this study, sterically invariant carborane-based chalcogenols were used as ligands for the formation of photoluminescent copper(I)-based metal-organic chalcogenolate assemblies (MO-CHAs). By precisely tuning the carborane dipole through isomer changes, control over MOCHA morphology and regulation of photophysical properties were achieved. Additionally, microcrystal electron diffraction (MicroED) was shown to be a powerful tool for elucidating metal chalcogenide structures, revealing a novel Cu4Se4 geometry in one isolated material.