LAUSR

Excited-state intramolecular proton transfer (ESIPT) has been widely employed for the design of a variety of functionality-led molecular systems. However, precise manipulation of the excited-state reaction is challenging. Herein, we report a new tactic for tuning ESIPT via incorporating an excited-state intramolecular charge transfer (ESICT) process. Specifically, three o-carborane derivatives, NaCBO, PaCBO, and PyCBO, were designed, where the 2-(2'-hydroxyphenyl)-benzothiazole is a typical ESIPT unit functioning as an electron acceptor, and the electron-donating units are naphthyl-(Na), phenanthrenyl-(Pa), and pyrenyl-(Py), respectively. The architectures of the molecules are featured with a face-to-face alignment of the two units. Spectroscopy and theoretical calculation studies revealed that the electron-donating capacity of the donors and solvent polarity continuously modulate the ESIPT/ESICT energetics and dynamics, resulting in distinct emissions. Moreover, the molecules depicted not only highly porous structures but also very different fluorescent colors in the solid state, enabling highly selective film-based fluorescence sensing of mustard gas simulant, 2-chloroethyl ethyl sulfide, with a detection limit of 50 ppb and a response time of 5 s. This work thus provides a reliable strategy for the creation of high-performance sensing fluorophores via ESIPT manipulation.