Intrinsic Multicolor Emissive Aliphatic Linear Polyphosphate Esters From the Charge‐Transfer‐Induced Enhanced Spatial Electronic Communication

Abstract Unconventional fluorescent polymers are attracting increasing attention because of their excellent biocompatibility and wide applications. However, these polymers typically exhibit weak long‐wavelength emission. Herein, three novel aliphatic linear polyphosphate esters are prepared via a one‐pot polycondensation reaction. Such polymers can generate strong blue, green, yellow, and red fluorescence under different excitations. Experimental and theoretical results showed that the cluster of C═C and phosphate ester groups attracted the negative charge of isolated functional groups, and the alkane chains and hydrogen atoms also provided a negative charge for spatial electronic communication. Then, intrinsic fluorescence arises from the charge‐transfer‐induced enhanced spatial electronic communication. Additionally, these polymers show potential applications in fluorescence film, ion detection, bacteria imaging, and visualization of the NaCl crystallization process. This work provides a universal design strategy for developing strong long‐wavelength emissive polymers and gains new insight into intrinsic emission mechanisms.