Fluorenyl radicals stabilized by donor-π-radical conjugation be-tween
nitrogen atoms and carbon radicals
Abstract
A design strategy towards stable fluorenyl radicals (FRs) is established
by introducing donor-π-radical (D-π-R) conjugation between amine N atoms
and FR centers through phenyl or 9-anthryl moieties. Four FRs with or
without N atom containing protecting groups were designed and
synthesized for comparison. X-ray crystallographic analysis displayed
planar fluorenyl skeletons of CDP-FR and MA-FR, which form large
dihedral angles with protecting groups. Even though, the increased
bond-order of C-C and C-N bond be-tween radical center and N atoms by
Wiberg bond analysis of all FRs confirmed the D-π-R conjugation.
Time-dependent DFT calcula-tions based on frontier molecular orbital
analysis further revealed the contribution of D-π-R structures as
donor-acceptor effect on the lowest energy absorptions of carbazole and
diphenylamine substituted CDP-FR and DPAA-FR. Therefore, beneficial from
D-π-R conjugations, CDP-FR and DPAA-FR showed better photo-stability
than TP-FR and MA-FR. Our study here provides a new strategy to design
and synthesize persistent stable monoradicals.