Supramolecular photoswitch with white-light emission based on bridged bis(pillar[5]arene)s

White light-emitting (WLE) switches have greatly promising and worthy applications in the field of controllable lighting, display, and sensing. Here, we unprecedentedly construct a photocontrollable light-harvesting supramolecular nanoassembly ( G/H@NiR ) with rarely switchable white light emission, which comprised oligo(phenylenevinylene)-bridged pillar[5]arenes ( H ), photochromic diarylethene ( G ), and Nile red ( NiR ), through host–guest complexation. In the nanosystem, color-tunable photoluminescence such as cyan, orange red, and especially white with chromaticity coordinates (0.33, 0.34) is achieved through altering the proportions of the energy donor (H in assembly G/H ) and acceptor center ( NiR ). Importantly, G , acting as a modulator, can controllably change the energy-transfer (ET) pathway between H and NiR , when the G/H@NiR nanoassembly was exposed to distinct light, achieving reversible switching of multicolor photoluminescence including white-light emission. In addition, the designed intelligent supramolecular assembly G/H@NiR with captivating characteristics has extremely valuable application as erasable multicolor fluorescent inks to be filled in the groove of a three-dimensional model and further form a high-security-level chromatic anticounterfeiting quick response (QR) code, which can be completely hidden and revealed under stimulation of distinct light. Besides, the erasable fluorescent inks can also be used to record data information in mixed fiber film, which can be completely wiped off and rerecord by distinct light. The study provides a controllable supramolecular light-harvesting strategy (the photo-modulating ET pathway in the light-harvesting process) for developing photo-responsive intelligent photoluminescence materials, particularly photosensitive WLE materials, possessing potential applications in photosensitive lighting and display, multicolor imaging, light-manipulative data storage, and high-security-level anticounterfeiting. • A photocontrollable light-harvesting supramolecular nanosystem is developed. • Color-tunable photoluminescence, especially white-light emission, is presented. • Photosensitive white-light emission is achieved. • The energy-transfer pathway in the light-harvesting process can be modulated by distinct light.