Unconventional Luminescence Polymer with Color‐Tunability based on Solvent‐induced Electrostatic Potential Distribution of Fluorophore

Abstract Tuning full‐color emission of polymers holds significant promise. However, preparing unconventional luminescence polymers with color‐tunability in dilute solution and understanding the relationship between non‐covalent interactions and luminescent behavior remains a great challenge. We report two emitters (P1 and P2) incorporating tetracoordinate boron. The P1 with non‐conjugated D‐π‐A structure, exhibited red delayed fluorescence at 645 nm with quantum yield of 9.15 % in aggregates. Notably, the emission wavelength of P1 can be tuned from 418 to 588 nm at different solvent. Similarly, the emission wavelength of P2 can also be adjusted by manipulating the interactions between the solvent and fluorophore. Experimental characterization and theoretical calculations indicate that the B←N bond and electronic interactions between solvent and fluorophore significantly regulate the equilibrium the electrostatic potential (ESP) and the intramolecular O⋅⋅⋅O interactions of P1, thereby modulating its emission wavelength. Additionally, these polymers showed excellent potential in fluoride ions detection. This work provides new insights into the complex effects of intermolecular interactions on luminescent properties.