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SELF-ASSEMBLED MONOLAYERS

A not-so-strong bond

Nature Reviews Materials volume 4, page 226 (2019)Cite this article

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Self-assembled monolayers (SAMs) of organic molecules provide inexpensive and versatile surface coatings for applications ranging from biology to electrochemistry. When the substrate is a noble metal, thiol (–SH) moieties are commonly used as end groups because of the strong affinity of sulfur with metals. Conventional wisdom describes the thiol moieties as chemisorbed to planar gold surfaces, with the loss of hydrogen during the formation of the bond. Writing in Nature Chemistry, Latha Venkataraman and colleagues now reveal that in gold–thiol SAMs, the gold–sulfur coupling unexpectedly has a physisorbed character.

Venkataraman and colleagues combined single-molecule junction conductance measurements and density functional theory calculations to investigate the bonding, studying junctions formed by molecules comprising thiol, thioether (–SMe) and pre-formed gold-thiolate (–SAuR) linkers attached to a Au(111) surface. They found that chemisorbed bonds only form when an excess of molecules are present around high-energy, uncoordinated gold atoms, which are rare on the planar Au(111) surface on which the bonding predominantly has physisorbed character. “Critically, we show that in dithiol-based SAMs formed from solution, the gold–sulfur coupling has a physisorbed rather than chemisorbed character, in stark contrast to the accepted view,” comments Venkataraman.

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  1. Nature Reviews Materials http://www.nature.com/natrevmats/

    Giulia Pacchioni

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  1. Giulia Pacchioni
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Correspondence to Giulia Pacchioni.

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Pacchioni, G. A not-so-strong bond. Nat Rev Mater 4, 226 (2019). https://doi.org/10.1038/s41578-019-0094-3

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