Nucleation products of ligated nanoclusters unaffected by temperature and reducing agentElectronic supplementary information (ESI) available: Experimental details, ESI-MS spectrum of complexes, assayed gold solutions reduced with NaBH4, and scattering fits are provided. See DOI: 10.1039/c2nr31661g

Atomically uniform nucleation products of ligated metal nanoclusters are observed irrespective of reduction conditions for metal-bidentate ligand systems. Monodentate ligands are not reported to wield similar control, indicating steric contributions of complexing ligands may be as important as their electronic structure for synthesizing small nanoclusters. Uniform metal nanoclusters can be synthesized and preserved through ligand-controlled assembly (nucleation) of reduced metal-bidentate ligand complexes.