Confirmation of a de novo structure prediction for an atomically precise monolayer-coated silver nanoparticle

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Science Advances  25 Nov 2016:
Vol. 2, no. 11, e1601609
DOI: 10.1126/sciadv.1601609


Fathoming the principles underpinning the structures of monolayer-coated molecular metal nanoparticles remains an enduring challenge. Notwithstanding recent x-ray determinations, coveted veritable de novo structural predictions are scarce. Building on recent syntheses and de novo structure predictions of M3AuxAg17−x(TBBT)12, where M is a countercation, x = 0 or 1, and TBBT is 4-tert-butylbenzenethiol, we report an x-ray–determined structure that authenticates an a priori prediction and, in conjunction with first-principles theoretical analysis, lends force to the underlying forecasting methodology. The predicted and verified Ag(SR)3 monomer, together with the recently discovered Ag2(SR)5 dimer and Ag3(SR)6 trimer, establishes a family of unique mount motifs for silver thiolate nanoparticles, expanding knowledge beyond the earlier-known Au-S staples in thiol-capped gold nanoclusters. These findings demonstrate key principles underlying ligand-shell anchoring to the metal core, as well as unique T-like benzene dimer and cyclic benzene trimer ligand bundling configurations, opening vistas for rational design of metal and alloy nanoparticles.

  • Atomically precise ligand-protected nanoclusters
  • silver nanoclusters
  • de novo structure prediction
  • x-ray structure determination
  • first-principles DFT calculations
  • optical absorption measurements and TDDFT calculations
  • electronic shell strcture
  • ligand bundling
  • interligand conformations
  • capping ligand mounts

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