The dual-emissive properties of solid-state difluoroboron β-diketonate-poly(lactic acid) (BF2bdkPLA) materials have been utilized for biological oxygen sensing. In this work, BF2dbm(X)PLA materials were synthesized, where X = H, F, Cl, Br, and I. The effects of changing the halide substituent and PLA polymer chain length on the optical properties in dilute CH2Cl2 solutions and solid-state polymer films were studied. These luminescent materials show fluorescence, phosphorescence, and lifetime tunability on the basis of molecular weight, as well as lifetime modulation via the halide substituent. Short BF2dbm(Br)PLA (6.0 kDa) and both short and long BF2dbm(I)PLA polymers (6.0 or 20.3 kDa) have fluorescence and intense phosphorescence ideal for ratiometric oxygen sensing. The lighter halide-dye polymers with hydrogen, fluorine, and chlorine substitution have longer phosphorescence lifetimes and can be utilized as ultrasensitive oxygen sensors. Photostability was also analyzed for the polymer films.
