Geometric and Electronic Structures of Boron(III)-Cored Dyes Tailored by Incorporation of Heteroatoms into Ligands

Complexation of a boron atom with a series of bidentate heterocyclic ligands successfully gives rise to corresponding BF2‐chelated heteroarenes, which could be considered as novel boron(III)‐cored dyes. These dye molecules exhibit planar structures and expanded π‐conjugated backbones due to the locked conformation with a boron center. The geometric and electronic structures of these BF2 complexes can be tailored by embedding heteroatoms in the unique modes to form positional isomer and isoelectronic structures. The structure–property relationship is further elucidated by studying the photophysical properties, electrochemical behavior and quantum‐chemical calculations. Tailor‐made: The geometric and electronic structures of novel boron(III)‐cored dyes 1–4 can be finely tailored by embedding heteroatoms in the unique modes to form positional isomer and isoelectronic structures.