Precursor-driven synthesis of copper nanoparticles: bridging experiment and theory in nuclearity effects

The synthesis of copper nanoparticles via hydrogenolysis of copper amidinate complexes is highly sensitive to the molecular structure of the precursor. This study demonstrates that the precursor's electronic structure, including its propensity to form higher-nuclearity copper assemblies, governs nanoparticle morphology and size distribution. Density Functional Theory (DFT) analyses, including Electron Localization Function (ELF), Atoms in Molecules (AIM) and Conceptual DFT (CDFT), provide theoretical insights into the Cu-Cu and Cu-N interactions and atomic properties. While experimental results establish the pivotal role of the precursor, detailed related modelling analyses reveal that the preferred nuclearity of the precursor in solution governs nanoparticle growth mechanisms. This work underscores the value of a holistic understanding of precursor properties to achieve rational design and control of nanoparticle syntheses.