Multicomponent synthesis of stereogenic-at-boron fluorophores (BOSPYR) from boronic acids, salicylaldehydes, and 2-formylpyrrole hydrazones

Abstract

This work describes one-step syntheses of various stereogenic-at-boron fluorochromes (BOSPYR) via multicomponent reactions involving readily accessible boronic acids, salicylaldehydes, and 2-formylpyrrole hydrazones. The dyes absorb and emit in the visible region of the electromagnetic radiation, and are characterized by large Stokes shifts (2850–4930 cm⁻¹) with weak fluorescence emissions (Φ_fl: 1.5–9.1%). Notably, the dimmed fluorescence of BOSPYRs recovers upon transition to viscous media (21-fold for 1a). The representative compound 1a exhibits clear Cotton effects with dissymmetry factors of ca. |g_abs| ∼ 1.9 × 10⁻³ in the visible region, indicating efficient asymmetry induction to the chromophore. The X-ray molecular structure of 1a shows that the chromophore deviates from planarity by 17.2°, which may contribute significantly to the inherent chirality of the fluorophore. A computational examination of excited states by time-dependent density functional theory (TD-DFT) identifies the emission mechanism as arising from a locally-excited (LE) state.