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.

自组装单分子层 (SAM) 广泛用于设计金属的表面特性。金属-硫醇盐键的相对简单和通用的化学性质使硫醇盐 SAM 成为一系列应用中的首选，但其易碎性和在空气中氧化的倾向限制了它们的长期使用。在这里，我们报告了二醇醚的无硫醇自组装单层和双层的形成，它们通过二醇醚官能化富勒烯的自发化学吸附与造币金属表面结合。所制备的组件是在基板和环境界面处呈现富勒烯笼的双层。随后暴露于官能化二醇醚会取代最顶层的二醇醚官能化富勒烯，并且所得组件将官能团暴露于环境界面。这些层表现出硫醇盐 SAM 的关键特性，但它们在环境条件下可稳定数周，如由烷基官能化二醇醚的 SAM 形成的隧道结的性能所示。加入混合单层的乙二醇醚官能化螺吡喃导致可逆的光驱动电导转换。乙二醇醚的自组装是硫醇盐 SAM 的直接替代品，它保留了所有有用的特性，同时避免了金属-硫醇键的缺点。光驱动电导开关。乙二醇醚的自组装是硫醇盐 SAM 的直接替代品，它保留了所有有用的特性，同时避免了金属-硫醇键的缺点。光驱动电导开关。乙二醇醚的自组装是硫醇盐 SAM 的直接替代品，它保留了所有有用的特性，同时避免了金属-硫醇键的缺点。