Synthesis, structures and electrochemical and photophysical properties of anilido-benzoxazole boron difluoride (ABB) complexes

Abstract

A new series of four-ring-fused π-conjugated anilido-benzoxazole boron difluoride (ABB) dyes were synthesized by employing an unsymmetrical bidentate ligand under a mild reaction condition. X-ray structural analysis demonstrated that the four-ring-fused π-conjugated skeleton is nearly coplanar, and almost orthogonal to the side anilido phenyl group with dihedral angles of 74–86°. The synthesized complexes exhibit very bright luminescence in solution (Φ_f = 0.45–0.96 in CH₂Cl₂) and in the solid-state (Φ_f = 0.07–0.37). These complexes show a larger Stokes shift (56–128 nm) than the well-known boron dipyrromethene dyes (8–12 nm, in most cases). The role of molecular packing patterns elucidated by the assistance of their X-ray crystal structures rationalizes the solid-state fluorescence. One of the tested compounds displayed aggregation induced emission (AIE). First-principle-based quantum-chemical studies were carried out on complexes 1–6. Time-dependent DFT (TD-DFT) calculations support the experimental results. The participation of the anilido phenyl moiety and the fluorine atoms was found to be negligible in the LUMO orbitals.