Issue 15, 2023

Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction

Abstract

We report here a novel family of boraolympicenes, structurally featuring boron-doping at the concave 11a-position of their π-skeletons and synthetically prepared via a facile one-pot triply borylation-based double-fold borocyclization reaction. Despite having no bulky protecting groups, these boraolympicenes exhibit excellent chemical stability against air and moisture, ascribed to the significant π-electron delocalization over the vacant pz orbitals of boron atoms as evidenced by both single-crystallographic and theoretical analyses. More importantly, the modular synthesis of these boraolympicenes allows the fine-tuning of their physicochemical properties, endowing them with intriguing electronic features, such as intense visible-to-NIR absorption and low-lying LUMO energy levels (∼−3.8 eV) as well as tunable molecular stacking characteristics in the crystalline state. As a model compound, a radical-anion salt of 6-phenyl-11a-boraolympicene was further generated through chemical reduction and well characterized by UV-vis-NIR absorption, ESR, and IR spectroscopy. This radical anion salt is sensitive to air and moisture but shows persistent stability under inert conditions benefiting from its stable borataalkene-containing resonant form.

Graphical abstract: Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
19 Jan 2023
Accepted
03 Mar 2023
First published
07 Mar 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 4158-4165

Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction

J. Guo, K. Zhang, Y. Wang, H. Wei, W. Xiao, K. Yang and Z. Zeng, Chem. Sci., 2023, 14, 4158 DOI: 10.1039/D3SC00342F

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