One/Two‐Photon‐Excited ESIPT‐Attributed Coordination Polymers with Wide Temperature Range and Color‐Tunable Long Persistent Luminescence

The multiple metastable excited states provided by excited‐state intramolecular proton transfer (ESIPT) molecules are beneficial to bring temperature‐dependent and color‐tunable long persistent luminescence (LPL). Meanwhile, ESIPT molecules are intrinsically suitable to be modulated as D‐π‐A structure to obtain both one/two‐photon excitation and LPL emission simultaneously. Herein, we report the rational design of a dynamic CdII coordination polymer (LIFM‐106) from ESIPT ligand to achieve the above goals. By comparing LIFM‐106 with the counterparts, we established a temperature‐regulated competitive relationship between singlet excimer and triplet LPL emission. The optimization of ligand aggregation mode effectively boost the competitiveness of the latter. In result, LIFM‐106 shows outstanding one/two‐photon excited LPL performance with wide temperature range (100–380 K) and tunable color (green to red). The multichannel radiation process was further elucidated by transient absorption and theoretical calculations, benefiting for the application in anti‐counterfeiting systems. One/two‐photon‐excited long persistent luminescence (LPL) was obtained in an ESIPT‐attributed CdII coordination polymer (LIFM‐106) with wide temperature range (100–380 K) and color tunability. Comparative study manifests the rational ligand modification and J‐aggregation in LIFM‐106 enhances the competitiveness of monomer LPL to counter‐balance the excimer emission.