Understanding seed-mediated growth of gold nanoclusters at molecular level

The continuous development of total synthesis chemistry has allowed many organic and biomolecules to be produced with known synthetic history-that is, a complete set of step reactions in their synthetic routes. Here, we extend such molecular-level precise reaction routes to nanochemistry, particularly to a seed-mediated synthesis of inorganic nanoparticles. By systematically investigating the time-dependent abundance of 35 intermediate species in total, we map out relevant step reactions in a model size growth reaction from molecularly pure Au₂₅ to Au₄₄ nanoparticles. The size growth of Au nanoparticles involves two different size-evolution processes (monotonic LaMer growth and volcano-shaped aggregative growth), which are driven by a sequential 2-electron boosting of the valence electron count of Au nanoparticles. Such fundamental findings not only provide guiding principles to produce other sizes of Au nanoparticles (e.g., Au₃₈), but also represent molecular-level insights on long-standing puzzles in nanochemistry, including LaMer growth, aggregative growth, and digestive ripening.Synthetic nanochemistry currently lacks the molecular step-by-step routes afforded to organic chemistry by total synthesis. Here, the authors track the seeded growth of atom-precise gold nanoclusters using mass spectrometry, revealing that the clusters evolve through a series of intermediates in two-electron steps.