A 1-Hydroxy-1H-imidazole ESIPT Emitter Demonstrating anti-Kasha Fluorescence and Direct Excitation of a Tautomeric Form

The ability of 1-hydroxy-1H-imidazoles to exist in the form of two prototropic tautomers, the N-hydroxy and the N-oxide forms, can be utilized in the design of new types of ESIPT-fluorophores (ESIPT=excited state intramolecular proton transfer). Here we report the first example of 1-hydroxy-1H-imidazole-based ESIPT-fluorophores, 1-hydroxy-5-methyl-2,4-di(pyridin-2-yl)-1H-imidazole (HL), featuring a short intramolecular hydrogen bond O-H...N (O...N 2.56 angstrom) as a pre-requisite for ESIPT. The emission of HL originates from the anti-Kasha S-2 -> S-0 fluorescence in the N-oxide form as a result of a large S-2-S-1 energy gap slowing down the S-2 -> S-1 internal conversion. Due to an energy barrier between the N-hydroxy and N-oxide forms in the ground state, the HL molecules can be trapped and photoexcited in the N-oxide form leading to the Stokes shift of ca. 60 nm which is the smallest among known ESIPT-fluorophores.