Copper-Phosphonate Lamella Intermediates Control the Shape of Colloidal Copper Nanocrystals

Understanding the structure and behavior of intermediates in chemical reactions is key to developing greater control over the reaction outcome. This principle is particularly important in the synthesis of metal nanocrystals (NC), where the reduction, nucleation and growth of the reaction intermediate will determine the final size and shape of the product. The shape of metal NCs plays a major role in determining their catalytic, photochemical and electronic properties and, thus, the potential applications of the material. In this work, we demonstrate that layered coordination polymers, called lamellae, are reaction intermediates for Cu NCs. Importantly, we discover that the lamella structure can be fine-tuned using organic ligands of different length and that these structural changes control the shape of the final NC. Specifically, we show that short-chain phosphonate ligands generate lamellae that are persistent enough at the reaction temperature to facilitate the soft-templating of Cu nuclei into anisotropic Cu NCs, being primarily triangular plates. In contrast, lamellae formed from long-chain ligands lose their structure and form spherical Cu NCs. The synthetic approach presented here provides a versatile tool for the future development of metal NCs, including other anisotropic structures.