N,O-Bidentated difluoroboron complexes based on pyridine-ester enolates: Facile synthesis, post-complexation modification, optical properties, and applications

Abstract

An array of pyridine-ester enolate based organoboron complexes has been designed and synthesized via a one-pot cascade of Pd-catalyzed α-arylation and BF2 complexation. The rapid structure-activity relationship (SAR) studies indicated that unsymmetrical N,O-chelated BF2 complexes were highly fluorescent in solid state, and exhibited large Stokes shifts, excellent photostability, along with insensitivity to pH. The α-aryl group could not only modulate the electronic effect but also inhibit the intermolecular π-π stacking to promote the aggregation-induced emission (AIE) effect. DFT calculations and experiments identified that the intramolecular charge transfer properties of these N,O-chelates could be switched by the modification of substituents, resulting tunable fluorescence wavelengths. Furthermore, post-complexation modification was accomplished, including Suzuki-Miyaura cross-coupling, Buchwald-Hartwig amination, oxidative cleavage, along with a unique triple substitution reaction involving propargyl Grignard reagents. The exemplificative application of dimethylamine substituted boron complex as a reversible acidic vapor sensor was also demonstrated.