Boron-doped double [6]carbohelicenes: a combination of helicene and boron-doped π-systems

Abstract

Helicenes, featuring unique helical structures, have a long history as three-dimensional polycyclic aromatic hydrocarbons (PAHs). Incorporation of heteroatoms into helicenes may alter their electronic structures and achieve unexpected physical properties. Here, we disclose fusion of boron-doped π-systems onto helicenes as an efficient strategy to design boron-doped carbohelicenes. Two boron-doped double [6]carbohelicenes were synthesized, which possess the C₅₈B₂ and C₈₆B₂ polycyclic π-skeletons containing two [6]helicene subunits, respectively. The C₈₆B₂ molecule thus represents the largest-size helicene-based boron-doped PAH. A thorough investigation reveals that the helicene moieties and boron atoms endow the polycyclic π-systems with delocalized electronic structures, and well-tunable ground-state and excited-state photophysical properties. It is notable that the C₅₈B₂ molecule displays excited-state stimulated emission behavior and amplified spontaneous emission (ASE) properties in not only the blend films with various doped concentrations but also the pure film. To our knowledge, it is the first example of ASE-active [n]helicene (n ≥ 6), and moreover, such robust ASE performance has rarely been observed in PAHs, demonstrating the promising utility of boron-doped carbohelicenes for laser materials.