Here we develop a high-performance approach to photoswitching, by exploiting singlet manifold photoredox between azobenzenes and covalently attached auxiliary chromophores. This enables well-penetrating red/NIR light of 630-740 nm, to which azobenzenes usually do not respond, to perform Z→E photoisomerisation that is also 100% complete and highly photon-efficient. Crucially, this process... Show more