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

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-BF 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 BF 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-BF 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 ()/()-enantiomers after optical resolution. This complex exhibited circular dichroism with a || of up to 1.2 × 10 and circularly polarized luminescence with a || on the order of 10 in solution and polymer film.