Diarenofuran[b]-fused BODIPYs: One-Pot SNAr-Suzuki Synthesis and Properties.

Abstract

We present a streamlined methodology that integrates regioselective tetrahalogen-BODIPY and o-hydroxyphenylboronic acid in a one-pot process, leveraging S_NAr nucleophilic substitution in conjunction with Suzuki coupling to afford diarenofuran [b]-fused BODIPYs (DBFB1-9) with commendable yields (85-95%) and short reaction times (0.5-1.0 h). X-ray structure analyses of DBFB5,7-9 elucidate that these diarenofuran[b]-fused BODIPYs adopt a "butterfly" conformation, maintaining a highly rigid planarity. A comprehensive examination of the spectroscopic and electrochemical properties of these diarenofuran[b]-fused BODIPY derivatives, incorporating various substituents, reveals intriguing characteristics, including pronounced absorption and emission in the near-infrared region (NIR), elevated fluorescence quantum yields (Φ_F = 75-89% in dichloromethane), and tunable HOMO-LUMO levels. Remarkably, compared to DBFB1-8, DBFB9 possesses a large extended π-conjugated system, resulting in significant red shifts in its absorption and emission maxima, reaching 623 and 635 nm, respectively, and a reduced HOMO-LUMO gap. Despite this substantial structural expansion, DBFB9 maintains a surprisingly high fluorescence quantum yield (Φ_F = 80%), underscoring its exceptional photophysical performance and strong potential for applications requiring efficient NIR emission and robust fluorescence retention.