Supramolecular Purely Organic Room-Temperature Phosphorescence

In recent years, purely organic room-temperature phosphorescence (RTP) has aroused wide concern and promotes the development of the supramolecular phosphorescence. Different from organic crystallization, polymerization, or matrix rigidification, supramolecular strategy mainly takes advantage of the synergy between supramolecular co-assembly and strong binding by macrocyclic host compounds (cucurbit[n]urils, cyclodextrins, etc.) to overcome deficiencies such as poor processability and water solubility and improves RTP materials' quantum efficiency and lifetime in the solid state or in an aqueous solution. Meanwhile, it expands application, especially in aqueous solution, in cell imaging. Therefore, supramolecular phosphorescence will become a new growth point and will have broad application prospects in chemistry, biology, and material science.This Account focuses on the uniquely synergetic advantages of co-assembly and host-guest interaction from macrocyclic hosts for enhancing RTP. This Account starts with a brief introduction of the recent development of organic RTP materials as well as the host-guest interaction and co-assembly. Then, we introduce a supramolecular solid-state RTP strategy involving an ultrahigh phosphorescent quantum yield via the tight encapsulation of macrocyclic host cucurbit[6]uril, an ultralong lifetime via changing the substituents of phosphors, and long-lived and bright RTP by the synergy of host-guest interaction and polymerization. Meanwhile, the applications of solid-state RTP materials for anti-counterfeiting and data encryption are presented. The third part will be the water-phase supramolecular phosphorescence systems constructed by water-soluble macrocyclic host cucurbit[8]uril. Host-guest interaction and polymerization worked together toward efficient phosphorescence in aqueous solution, and the multi-stage assembly promoted phosphorescent applications such as cell targeted imaging and energy transfer. A humidity sensor and data encryption by the conversion of supramolecular hydrogels and xerogels are also involved. In the summary section, we present perspectives and possible research directions for supramolecular phosphorescence.Furthermore, on the basis of previous research, we would like to conclude and propose the developing concept of "macrocycles enhance guest's phosphorescence", and this concept not only means that the macrocyclic host limits the movement of the guest compound or promotes interactions between guest compounds but also involves the synergetic enhancement centered on macrocyclic compounds via multi-stage supramolecular assembly which further improves the efficiency of RTP, water solubility, and biocompatibility. And we believe that this concept will be able, together with theory of "assembly-induced emission" and "aggregation-induced emission", to accelerate the development of purely organic RTP materials.