Premium
A Stable N ‐Annulated Perylene‐Bridged Bisphenoxyl Diradicaloid and the Corresponding Boron Trifluoride Complex
Author(s) -
Wei Haipeng,
Zhang Liyan,
Phan Hoa,
Huang Xiaobo,
Herng Tun Seng,
Zhou Jun,
Zeng Wangdong,
Ding Jun,
Luo Shenglian,
Wu Jishan,
Zeng Zebing
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701692
Subject(s) - density functional theory , boron trifluoride , chemistry , perylene , photochemistry , singlet state , lewis acids and bases , band gap , homo/lumo , spectroscopy , materials science , crystallography , computational chemistry , molecule , excited state , organic chemistry , physics , atomic physics , optoelectronics , quantum mechanics , catalysis
Organic π‐extended radicals display unique electronic structures, and could be used as promising functional materials. However, design and synthesis of stable radicals are challenging for chemists due to their high reactivity. In this work, we synthesized a stable N ‐annulated perylene‐bridged bisphenoxyl diradicaloid, and its complex with Lewis acid boron trifluoride. Their ground‐state geometric and electronic structures were systematically studied by various experimental methods, including X‐ray crystallographic analysis, variable‐temperature NMR spectroscopy, electron‐spin resonance spectroscopy (ESR), and superconducting quantum interference device (SQUID) measurements, supported by density functional theory. Both were observed as open‐shell singlet diradicaloids in the ground state. The bisphenoxyl diradicaloid demonstrated string features of strong near‐infrared (NIR) absorption, closely packed π‐dimer structure in crystals, amphoteric redox behavior with a small HOMO–LUMO energy band gap, and a rather small singlet‐triplet gap, whereas the complex showed very different photophysical, electrochemical, and magnetic properties. Our studies provide an efficient method of making stable diradicaloids by Lewis acid/base complexation.