1. Boron-Doped Polycyclic π-Electron Systems with an Antiaromatic Borole Substructure That Forms Photoresponsive B–P Lewis Adducts
- Author
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Ando, Naoki, Yamada, Takuya, Narita, Hiroki, Oehlmann, Niels N., Wagner, Matthias, and Yamaguchi, Shigehiro
- Abstract
Heteroatom doping is a powerful strategy to alter the electronic structure of polycyclic aromatic hydrocarbons (PAHs). Especially boron doping endows PAH scaffolds with electron-accepting character and Lewis acidic centers. Herein, we report that embedding a five-membered borole ring into a polycyclic skeleton imparts the π-system with antiaromatic character and thereby induces unique properties and behavior. A series of borole-embedded π-conjugated compounds were synthesized from teraryl precursors via a borylation/intramolecular electrophilic C–H borylation sequence. The obtained compounds exhibit planar structures with distorted geometries around the boron center and form columnar slipped face-to-face π-stacked structures. Among these compounds, a pyrene-fused derivative shows an intense emission with a high quantum yield in solution. This compound also exhibits high Lewis acidity, which reflects the antiaromatic character and strained structure of the borole substructure. This compound forms a Lewis acid–base adduct even with weakly Lewis basic phosphorus-containing polycyclic π-systems. Analyzing the crystal structure of the thus-obtained adduct revealed a complex between the boron- and phosphorus-embedded π-systems with a direct B–P dative bond. This complex undergoes photodissociation in the excited state and exhibits an emission exclusively from the base-free borole-embedded π-system.
- Published
- 2021
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