Acid/Base-Responsive Circularly Polarized Luminescence Emitters with Configurationally Stable Nitrogen Stereogenic Centers

A way to prevent the fast configurational interconversion of tertiary amines is to invoke Tröger's base analogs, which display methano- or ethano-bridged diazocine cores fused to aromatic rings. These derivatives are configurationally stable, even in acidic media when their structures bear ethylene bridges. Here, a two- to three-step synthesis is presented of methano- and ethano-bridged Tröger's base analogs with two peripheral fluorophores, i.e., anthracene, pyrene, and 9,9-dimethylfluorene units. These compounds, possessing two nitrogen stereogenic centers, exhibit good circularly polarized luminescence (CPL) dissymmetry factors (|g_lum| up to 1.2 × 10⁻³) and brightnesses (B_CPL up to 26.3 M⁻¹ cm⁻¹), as well as excellent fluorescence quantum yields, demonstrating the Tröger´s base core to be a convenient scaffold to prepare CPL emitters upon functionalization with simple achiral fluorophores. Furthermore, the configurationally stable ethano-bridged Tröger's base analogs are employed to modulate their CPL response, generating a CPL switch through their protonation/deprotonation by consecutive additions of acid and base. The reversibility of the switching process is demonstrated for two cycles without altering the CPL performance of the molecule. It is believed that this straightforward and efficient approach to building CPL emitters employing the Tröger's base core could lead to its incorporation in CPL-based sensors and materials.