Excited-State Intramolecular Proton Transfer-Based Multifunctional Solid-State Emitter: A Fluorescent Platform with Write-Erase-Write Function

The excited-state intramolecular proton transfer (ESIPT)-based molecular probes have drawn significant attention owing to their environment-sensitive fluorescence properties, large Stokes shift, and emerged as building blocks for the development of molecular sensors and switches. However, most of the ESIPT-based fluorophores exhibit weak emission in the solid state limiting the scope of real-time applications. Addressing such issues, herein, we presented a C-3 symmetric-like molecular architecture employing a simple one-step Schiff base condensation between triaminoguanidinium chloride and 3,5-di-tert-butyl-2-hydroxybenzaldehyde (TGHB). The temperature-dependent fluorescence studies including at 77 K indicated the strong emission from the keto tautomer compared to that of the enol tautomer. The facile ESIPT in TGHB in the solid-state led to a remarkable enhancement of fluorescence quantum yield of 1600 times compared to that of the solution (lambda(em) = 545 nm) by restricting the intramolecular rotation and subsequently suppressing the nonradiative deactivation. The excited-state processes were further elucidated through time-resolved fluorescence measurements. TGHB exhibited turn on-off fluorescence upon exposure to acid/base vapor in the form of a powder as well as a transparent, freestanding thin film. A rewritable and erasable fluorescent platform was demonstrated using TGHB as molecular ink, which offers a potential testbed for performing write-erase-write cycles multiple times. In addition, TGHB, possessing multiple binding sites (O and N donors) involving the central core of the triaminoguanidinium cation displayed selective turn-on fluorescence with Zn2+. The structure-property relationship revealed in the present study provides insight into the development of novel cost-effective multifunctional materials, which are promising for stimuli-responsive molecular switches.