Cluster-induced aggregation in polyurethane derivatives with multicolour emission and ultra-long organic room temperature phosphorescence

Non-conjugated luminescent polymers (NCLPs) have the advantages of simple synthesis, optical tunability, and excellent processability. However, the underlying luminous mechanism in NCLPs remains obscure and it is a considerable challenge to obtain NCLPs with ultra-long phosphorescence lifetime and multicolour emission simultaneously. In this article, linear polyurethane derivatives (PUs) with cluster-induced aggregation, multicolour luminescence and ultra-long phosphorescence have been prepared by simply adjusting the reaction temperature and the reaction time. DFT calculations and molecular dynamics simulations provide elaborate microstructural information on the PUs. With the synergistic effect of abundant hydrogen bonding interactions, through-space dative bonds, short interatomic contacts and oxygen clusters various luminous clusters are formed. The energy level splitting caused by clusters with different extents of spatial conjugation endows the NCLPs with multicolour clusteroluminescence, promotes intersystem crossing (ISC), and stabilises the triplet excited state, and finally an ultra-long room temperature phosphorescence (RTP) lifetime of 0.45 s is attained. Experimental encryption/decryption models validate the potential of the PUs in information security. The results have important implications for understanding the intrinsic mechanism of unconventional luminescence in the absence of any traditional conjugative units or heavy atom effects, and they provide a new horizon for the strategic design of multicolour luminescence and ultra-long phosphorescence in NCLPs for a range of practical applications. Cluster-induced aggregation, multicolour luminescence and ultra-long phosphorescence (0.45 s) in NCLPs based on polyurethane derivatives have been achieved by simply adjusting reaction temperature and reaction time; this is the longest reported phosphorescence lifetime for pure NCLPs.