Orthogonal switching of a single supramolecular complex

Orthogonal control over systems represents an advantage over mono-functional switches as both the nature and order of distinctly different stimuli manifest themselves in a wide array of outcomes. Host-guest complexes with multiple, simultaneously bound guests offer unique opportunities to address a set of 'on' and 'off' states accessible on demand. Here we report cucurbit[8]uril-mediated host-guest heteroternary complexes constructed with both redox- and light-responsive guests in a single, supramolecular entity. The complex responds to orthogonal stimuli in a controlled, reversible manner generating a multifunctional switch between a 'closed' heteroternary complex, a redox-driven 'closed' homoternary complex and a photo-driven 'open' uncomplexed state. We exploit both photochemical and electrochemical control over the supramolecular coding system and its surface wettability to demonstrate the system's complexity, which could be readily visualized on a macroscopic level, thus offering new opportunities in the construction of memory devices.