posted on 2017-06-01, 16:51authored byRyohei Kurata, Daisuke Sakamaki, Akihiro Ito
Diradical dications
of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene
(1) and 9,10-anthracenylene (2a) moieties
are embedded in their macrocyclic backbones were
successfully isolated as air-stable salts. The structures of 12+ and 2a2+ were elucidated
by X-ray analysis, and significantly different types of structural
deformation led to different spin density distributions due to the
steric demand of the confronted arene moieties. The singlet–triplet
energy gaps were determined to be +0.3 kcal mol–1 (+151 K) and −1.0 kcal mol–1 (−503
K) by SQUID measurements, indicating the triplet ground state for 12+ and the singlet ground state for 2a2+.