Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies
Harrison A. Mills, Christopher G. Jones, Kierstyn P. Anderson, Austin D. Ready, Peter I. Djurovich, Saeed I. Khan, J. Nathan Hohman, Hosea M. Nelson, Alexander M. Spokoyny
Abstract
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.