Oxidative control over the morphology of Cu₃(HHTP)₂, a 2D conductive metal-organic framework

The morphology of electrically conductive metal-organic frameworks strongly impacts their performance in applications such as energy storage and electrochemical sensing. However, identifying the appropriate conditions needed to achieve a specific nanocrystal size and shape can be a time-consuming, empirical process. Here we show how partial ligand oxidation dictates the morphology of Cu₃(HHTP)₂ (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), a prototypical 2D conductive metal-organic framework. Using organic quinones as the chemical oxidant, we demonstrate that partial oxidation of the ligand prior to metal binding alters the nanocrystal aspect ratio by over 60-fold. Systematically varying the extent of initial ligand oxidation leads to distinct rod, block, and flake-like morphologies. These results represent an important advance in the rational control of Cu₃(HHTP)₂ morphology and motivate future studies into how ligand oxidation impacts the nucleation and growth of 2D conductive metal-organic frameworks.