title: Stereoelectronic switching in single-molecule junctions.
abstract: A new intersection between reaction chemistry and electronic circuitry is emerging from the ultraminiaturization of electronic devices. Over decades chemists have developed a nuanced understanding of stereoelectronics to establish how the electronic properties of molecules relate to their conformation; the recent advent of single-molecule break-junction techniques provides the means to alter this conformation with a level of control previously unimagined. Here we unite these ideas by demonstrating the first single-molecule switch that operates through a stereoelectronic effect. We demonstrate this behaviour in permethyloligosilanes with methylthiomethyl electrode linkers. The strong σ conjugation in the oligosilane backbone couples the stereoelectronic properties of the sulfur-methylene σ bonds that terminate the molecule. Theoretical calculations support the existence of three distinct dihedral conformations that differ drastically in their electronic character. We can shift between these three species by simply lengthening or compressing the molecular junction, and, in doing so, we can switch conductance digitally between two states.
authors.affiliation: Department of Chemistry, Columbia University, New York 10027, USA.
authors.forename: Timothy A
authors.initials: TA
authors.lastname: Su
authors.affiliation: Department of Applied Physics, Columbia University, New York 10027, USA.
authors.forename: Haixing
authors.identifier: 0000000213834907
authors.initials: H
authors.lastname: Li
authors.affiliation: Department of Chemistry, Columbia University, New York 10027, USA.
authors.forename: Michael L
authors.initials: ML
authors.lastname: Steigerwald
authors.affiliation: Department of Applied Physics, Columbia University, New York 10027, USA.
authors.forename: Latha
authors.initials: L
authors.lastname: Venkataraman
authors.affiliation: Department of Chemistry, Columbia University, New York 10027, USA.
authors.forename: Colin
authors.initials: C
authors.lastname: Nuckolls