Enhancing corannulene chemiluminescence, electrochemiluminescence and photoluminescence by means of an azabora-helicene to slow down its bowl inversion

Abstract

Aromatic system extension of corannulene (Cor) is a synthetic challenge to access non-planar polyaromatic hydrocarbons (PAHs). Herein, we report the design and synthesis of azaborahelicene corannulene 1 through hybridization of an azabora[5] helical structure and subsequent luminescence studies. Significant enhancement in chemiluminescence (CL), electroluminescence (ECL) and photoluminescence (PL) is achieved compared to those of pristine Cor. Specifically, hybrid 1 shows a notable augmentation in absolute luminescence quantum efficiencies: 25-fold for CL, up to 23-fold for ECL with BPO as a coreactant, and 30-fold for PL, respectively, compared to those of pristine Cor. Intriguingly, the blue light emission observed in all three luminescence types suggests the presence of a single excited state. As revealed by variable-temperature (VT) ¹H NMR experiments, the bowl inversion frequency apparently decelerates by the steric effect of the helix motif in 1, which could contribute to the enhanced luminescent properties by reducing excited energy losses non-radiatively through fewer molecular motions; these enhanced luminescence observations could be categorized alongside the aggregation induced emission (AIE) and crystallization-induced emission (CIE) phenomena. This work not only provides fundamental insights into improved luminescence quantum efficiencies via strategic modulation of the molecular structure and geometry, but the work also reveals Cor's inherent potential to build efficient blue-light emitting materials and devices.