title: Confirmation of a de novo structure prediction for an atomically precise monolayer-coated silver nanoparticle.
abstract: 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 ofM3AuxAg17-x(TBBT)12, whereMis 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)3monomer, together with the recently discovered Ag2(SR)5dimer and Ag3(SR)6trimer, 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.
authors.affiliation: Department of Chemistry, University of Toledo, Toledo, OH 43606, USA.
authors.forename: Brian E
authors.identifier: 0000-0003-4880-1766
authors.initials: BE
authors.lastname: Conn
authors.affiliation: Department of Chemistry, University of Toledo, Toledo, OH 43606, USA.
authors.forename: Aydar
authors.identifier: 0000-0001-7146-2534
authors.initials: A
authors.lastname: Atnagulov
authors.affiliation: School of Solar and Advanced Renewable Energy, University of Toledo, Toledo, OH 43606, USA.
authors.forename: Bokwon
authors.identifier: 0000-0003-4615-4059
authors.initials: B
authors.lastname: Yoon
authors.affiliation: School of Physics, Georgia Institute of Technology, Atlanta, GA 30332-0430, USA.
authors.forename: Robert N
authors.identifier: 0000-0001-9600-4249
authors.initials: RN
authors.lastname: Barnett
authors.affiliation: School of Physics, Georgia Institute of Technology, Atlanta, GA 30332-0430, USA.
authors.forename: Uzi
authors.initials: U
authors.lastname: Landman
authors.affiliation: Department of Chemistry, University of Toledo, Toledo, OH 43606, USA.; School of Solar and Advanced Renewable Energy, University of Toledo, Toledo, OH 43606, USA.
authors.forename: Terry P
authors.initials: TP
authors.lastname: Bigioni
keywords: Atomically precise ligand-protected nanoclusters; capping ligand mounts; de novo structure prediction; electronic shell strcture; first-principles DFT calculations; interligand conformations; ligand bundling; optical absorption measurements and TDDFT calculations; silver nanoclusters; x-ray structure determination