Simultaneous discovery of chiral and achiral dyes: elucidating the optical functions of helical and flag-hinged boron tetradentate complexes

Abstract

The construction of novel complexes can lead to the manifestation of unexpected structures and properties, thereby making chemical exploration in experiments a potential source for novel discoveries. In this study, by reacting 6,6′-dihydrazineyl-2,2′-bipyridine with acyl chlorides and subsequently coordinating with boron trifluoride, two different boron-tetradentate ligand complexes were simultaneously generated. One of these complexes exhibited a unique structure in which tetra-BF₂ moieties coordinated to all four coordination sites of the ligand molecule, forming a flag-hinged structure around the bipyridine part. The second complex featured a helical structure formed by the hybridization of two BF₂ and one B–O–B moieties, representing a highly unusual form of the complex. The structures of these two boron complexes were consistently observed when various substituted acyl chlorides were employed. Furthermore, it was found that enhancing electron-donor properties could induce a redshift in emissions. Utilizing the dimethylamino group as the proton receptor promoted a yellow-to-blue fluorescence switch in the tetra-BF₂ complex and an OFF/ON fluorescence in the B–O–B bridged complex upon protonation. The helical chirality observed in the latter complex resulted in stable (P)/(M)-enantiomers after optical resolution. This complex exhibited circular dichroism with a |g_abs| of up to 1.2 × 10⁻² and circularly polarized luminescence with a |g_lum| on the order of 10⁻³ in solution and polymer film.