Mechanochromic Luminescence and Aggregation Induced Emission of Dinaphthoylmethane β‑Diketones and Their Boronated Counterparts

Mechanochromic luminescence has been observed in many boron coordinated β-diketonate (BF2bdk) complexes. Recently, it was shown that the metal-free methoxy-substituted dinaphthoylmethane β-diketone (dnmOMe) also displayed aggregation induced emission (AIE), solvatochromism, and high contrast mechanochromic luminescence (ML) that recovered rapidly at room temperature. In order to understand how substituents and boron coordination affect solution and solid-state optical properties, a series of methoxy- and bromo-substituted derivatives (dnm, dnmOMe, dnmBr, and dnmBrOMe) and their corresponding boron complexes (BF2dnm, BF2dnmOMe, BF2dnmBr, and BF2dnmBrOMe) were synthesized and their AIE, ML, and room temperature recovery properties were compared. All boron complexes exhibited red-shifted absorption and emission, in addition to larger solution and solid-state quantum yields than β-diketones. While AIE studies show increased emission for dnmOMe and dnmBrOMe, the emission of corresponding boron complexes diminished upon aggregation. However, boron complexes were still strongly emissive in the solid state. ML properties were investigated using spin-cast films. Smearing resulted in the appearance of blue-green emission in ligands and a color change from green to yellow-orange in boron complexes. Bromide substituted derivatives showed increased room temperature recovery times compared to other dnm ligands, and boron complexes show only partial recovery over several days.