TY - JOUR AU - Qiu, Xinkai AU - Ivasyshyn, Viktor AU - Qiu, Li AU - Enache, Mihaela AU - Dong, Jingjin AU - Rousseva, Sylvia AU - Portale, Giuseppe AU - Stöhr, Meike AU - Hummelen, Jan C. AU - Chiechi, Ryan C. T1 - Thiol-free self-assembled oligoethylene glycols enable robust air-stable molecular electronics JF - Nature Materials SP - 330 EP - 337 IS - 3 VL - 19 PY - 2020 AB - Self-assembled monolayers (SAMs) are widely used to engineer the surface properties of metals. The relatively simple and versatile chemistry of metal–thiolate bonds makes thiolate SAMs the preferred option in a range of applications, yet fragility and a tendency to oxidize in air limit their long-term use. Here, we report the formation of thiol-free self-assembled mono- and bilayers of glycol ethers, which bind to the surface of coinage metals through the spontaneous chemisorption of glycol ether-functionalized fullerenes. As-prepared assemblies are bilayers presenting fullerene cages at both the substrate and ambient interface. Subsequent exposure to functionalized glycol ethers displaces the topmost layer of glycol ether-functionalized fullerenes, and the resulting assemblies expose functional groups to the ambient interface. These layers exhibit the key properties of thiolate SAMs, yet they are stable to ambient conditions for several weeks, as shown by the performance of tunnelling junctions formed from SAMs of alkyl-functionalized glycol ethers. Glycol ether-functionalized spiropyrans incorporated into mixed monolayers lead to reversible, light-driven conductance switching. Self-assemblies of glycol ethers are drop-in replacements for thiolate SAMs that retain all of their useful properties while avoiding the drawbacks of metal–thiolate bonds. TS - BibTeX DO - 10.1038/s41563-019-0587-x M4 - Citavi ER -