Self-Sensitized and Reversible O 2 Reactivity with Bisphenalenyls for Simple, Tunable, and Multicycle Colorimetric Oxygen-Sensing Films.

Monitoring the levels of molecular oxygen (O 2 ) is critical for numerous applications, but there is still a long-standing challenge to develop robust and cost-effective colorimetric sensors that enable detection by changes in color. Current technologies employ chromophores that require additional additives, which inherently increase the cost and complexity. Here, we report that bisphenalenyls (PQPLs) function as the single active component for colorimetric O 2 sensing through their quantitative conversion into aromatic endoperoxides (EPOs). PQPLs display self-sensitizing reactivity: they are capable of generating singlet oxygen and binding it without the need for external photosensitizers. The rates of PQPL photooxygenation depend on the electron-donating ability of substituents, which highlights a simple strategy for tuning O 2 sensitivity. EPOs are stable under ambient conditions but can be thermally stimulated to convert back to PQPLs and concomitantly release O 2 . Polymer-supported (PTMSP) films of PQPLs (2 wt %) reproduce these reactivity trends with a rapid red-to-colorless transition that is visible to the naked eye within 1 h of exposure and show a very low limit of detection (<5 ppm O 2 ). Films are chemically and thermally robust and maintain up to >99% of their original colorimetric response when reused and subjected to multiple cycles of photooxygenation and O 2 release. The simplicity and solution processability of these materials highlight their potential as "intelligent" inks for printable colorimetric sensors.