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Stereoelectronic switching in single-molecule junctions

Nature Chemistry volume 7, pages 215–220 (2015)Cite this article

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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.

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Figure 1: Structures of oligosilanes Si1, Si4, Si7 and Si10 calculated at the B3LYP/6-31G** level.
Figure 2: Iterative synthesis of oligosilanes terminated with methylthiomethyl end groups.
Figure 3: Conductance analysis of the oligosilane series.
Figure 4: DFT calculations describe the mechanism for switching as the oligosilanes are elongated in the junction.

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Acknowledgements

We thank the National Science Foundation (NSF) for the primary support of these studies under Grant No. CHE-1404922. T.A.S. is supported by the NSF Graduate Research Fellowship under Grant No. 11-44155. H.L. is supported by the Semiconductor Research Corporation and New York Center for Advanced Interconnect Science and Technology program. L.V. thanks the Packard Foundation for support. We thank R. S. Klausen, P. Mortimer and Y. Itagaki for mass spectrometry assistance and O. Adak, E. J. Dell and J. L. Leighton for insightful discussions.

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Authors and Affiliations

  1. Department of Chemistry, Columbia University, New York, 10027, USA

    Timothy A. Su, Michael L. Steigerwald & Colin Nuckolls

  2. Department of Applied Physics, Columbia University, New York, 10027, USA

    Haixing Li & Latha Venkataraman

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  1. Timothy A. Su
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Contributions

T.A.S. synthesized all the molecules. H.L. carried out all the STM-BJ measurements. T.A.S. and M.L.S. carried out all the computations. All the authors conceived the idea, designed the experiments, analysed the data and co-wrote the manuscript.

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Correspondence to Michael L. Steigerwald, Latha Venkataraman or Colin Nuckolls.

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Su, T., Li, H., Steigerwald, M. et al. Stereoelectronic switching in single-molecule junctions. Nature Chem 7, 215–220 (2015). https://doi.org/10.1038/nchem.2180

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