On the Fine-Tuning of the Excited-State Intramolecular Proton Transfer (ESIPT) Process in 2-(2′-Hydroxybenzofuran)benzazole (HBBX) Dyes

5 years ago

On the Fine-Tuning of the Excited-State Intramolecular Proton Transfer (ESIPT) Process in 2-(2′-Hydroxybenzofuran)benzazole (HBBX) Dyes

Elodie Heyer, Karima Benelhadj, Simon Budzák, Denis Jacquemin, Julien Massue, Gilles Ulrich

Herein, a full investigation of the optical properties and first-principles calculations of a large series of original 2-(2′-hydroxybenzofuran)benzazole (HBBX) dyes is described. The electronic substitution on the π-conjugated core of the fluorophores and the nature of the heteroatom (O, S, N) was varied extensively to assess the necessary parameters to trigger a partial frustration of the excited-state intramolecular proton transfer (ESIPT) process, which results in the emission of both tautomers, that is, enol and keto (E* and K*). The optical properties, studied in solution and in the solid state, revealed the appearance of either an intense single K* or a dual E*/K* emission; a feature that is highly dependent on the electronic substitution (donating or accepting), the heteroelement, and the close environment. Subtle modifications of these parameters allowed the establishment of structure–property relationships that were successfully rationalized by first-principles calculations. In particular, the E*/K* emission intensity ratio was shown to be directly related to the free energies of the two emissive tautomers in the excited state. A study of frustration: A series of 2-(2′-hydroxybenzofuran)benzazole (HBBX) dyes has been prepared and studied. Their optical properties were shown to be highly dependent on the substitution and the close environment (see figure; EA=electron acceptor, ED=electron donor). These observations were rationalized by using first-principles calculations.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700299