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Reversible Self‐Assembling of Boryl Radical Anions to Their Diradicals with Tunable Singlet Ground States
Author(s) -
Feng Rui,
Zhang Li,
Chen Chao,
Fang Yong,
Zhao Yue,
Tan Gengwen,
Wang Xinping
Publication year - 2019
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.201804918
Subject(s) - diradical , chemistry , singlet state , photochemistry , electron paramagnetic resonance , potassium , excited state , borane , salt (chemistry) , organic chemistry , atomic physics , catalysis , nuclear magnetic resonance , physics
Two novel boron‐centered diradicals based on dimesitylpyridine borane ( 1 ) were synthesized by the self‐assembling of the corresponding radical sodium and potassium salts, respectively. The sodium diradical was obtained by re‐dissolving the crystals of the radical salt 1Na in toluene, while the potassium diradical was directly obtained by the reduction of 1 with potassium in THF. The diradicals could be converted back to their radical anions in THF solution, forming a reversible process. EPR spectroscopy and SQUID measurements, together with theoretical calculations, show that the diradicals have singlet ground states with excited triplet states. Their singlet–triplet energy gaps are tunable with metals.