Molecules provide versatile building blocks, with a vast palette of functionalities and an ability to assemble via supramolecular and covalent bonding to generate remarkably diverse macromolecular systems. This is abundantly displayed by natural systems that have evolved on Earth, which exploit both supramolecular and covalent protocols to create the machinery of life. Importantly, these molecular assemblies deliver functions that are reproducible, adaptable, finessed and responsive. There is now a real need to translate complex molecular systems to surfaces and interfaces in order to engineer 21st century nanotechnology. ‘Top-down’ and ‘bottom-up’ approaches, and utilisation of supramolecular and covalent assembly, are currently being used to create a range of molecular architectures and functionalities at surfaces. In parallel, advanced tools developed for interrogating surfaces and interfaces have been deployed to capture the complexities of molecular behaviour at interfaces from the nanoscale to the macroscale, while advances in theoretical modelling are delivering insights into the balance of interactions that determine system behaviour. A few examples are provided here that outline molecular behaviour at surfaces, and the level of complexity that is inherent in such systems.
Erratum: Competition between Covalent Bonding and Charge Transfer at Complex-Oxide Interfaces [Phys. Rev. Lett.112, 196802 (2014)]
