Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on Au(111)

Jiawei Yan, Runhai Ouyang, Palle Skovhus Jensen, Erhad Ascic, David Ackland Tanner, Bingwei Mao, Jingdong Zhang, Chunguang Tang, Noel S. Hush, Jens Ulstrup, Jeffrey R. Reimers

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The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstituted chiral alkanethiol), followed by in situ scanning tunneling microscopy (STM) imaging combined with density functional theory molecular dynamics STM image simulations. Even though butanethiol SAMs manifest strong headgroup interactions, steric interactions are shown to dominate SAM structure and chirality. Indeed, steric interactions are shown to dictate the nature of the headgroup itself, whether it takes on the adatom-bound motif RS•Au(0)S•R or involves direct binding of RS• to face-centered-cubic or hexagonal-close-packed sites. Binding as RS• produces large, organizationally chiral domains even when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS• also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs.
Original languageEnglish
JournalJournal of the American Chemical Society
Issue number49
Pages (from-to)17087-17094
Publication statusPublished - 2014


  • Adatoms
  • Binding sites
  • Chirality
  • Density functional theory
  • Molecular dynamics
  • Scanning tunneling microscopy
  • Stereochemistry
  • Stereoselectivity
  • Alkanethiols
  • Chiral centers
  • Close-packed
  • Direct bindings
  • Face-centered cubic
  • In-situ scanning tunneling microscopies
  • Steric interactions
  • Surface units
  • Self assembled monolayers


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