jp8b00515_si_001.pdf (1.64 MB)
A Study on the Origin of the Radical in Fullerene and Graphene
journal contribution
posted on 2018-04-04, 00:00 authored by Ling Li, Yuan LiWe
reported the electron spin resonance (ESR) signal in neutral
low band gap semiconductors and C60 in the Li Y., J. Phys. Chem.
C 2017, 121, 8579–8588. Herein, further investigation
on the origin of the radical of fullerene and its derivatives was
conducted, and we proposed an open-shell diradical ground state of
C60 and its derivatives for the first time in this work.
The radicals of fullerene are usually acknowledged as their impurities
or radical cations/anions. Diradical ground states in polycyclic aromatic
hydrocarbons including the zethrene family and others with fused five-/six-member
rings motivate us to investigate the other potential origin of the
radicals of fullerene. C60 has 1812 sets of resonance structures,
which is the key factor to stabilize its diradicals. Numerous sets
of resonance structures and excellent electron delocalization of graphene
play as the key factors in stabilizing its diradicals. The previously
claimed ESR-silent C60 after sublimation is due to the
four-member ring formation and further self-polymerization. C60 with higher purity exhibited a higher ESR signal intensity,
and this further confirmed that the ESR might not come from the impurity.
Previously published work confirmed the radical is not from a radical
cation/anion; our proposal of the radical of fullerene is reasonable
in understanding its basic properties. Moreover, the radical origin
of graphene is also proposed similarly.