Phenalenyl,
a zigzag-edged odd alternant hydrocarbon unit can be
found in the graphene nanosheet. Hückel molecular orbital calculations
indicate the presence of a nonbonding molecular orbital (NBMO), which
originates from the linear combination of atomic orbitals (LCAO) arising
from 13 carbon atoms of the phenalenyl molecule. Three redox states
(cationic, neutral radical, and anionic) of the phenalenyl-based molecules
were attributed to the presence of this NBMO. The cationic state can
undergo two consecutive reductions to result in neutral radical and
anionic states, stepwise, respectively. The phenalenyl-based radicals
were found as crucial building blocks and attracted the attention
of various research fields such as organic synthesis, material science,
computation, and device physics. From 2012 onward, a strategy was
devised using the cationic state of phenalenyl-based molecules and
in situ generated phenalenyl radicals, which created a new domain
of catalysis. The in situ generated phenalenyl radicals were utilized
for the single electron transfer (SET) process resulting in redox
catalysis. This emerging range of applications rejuvenates the more
than six decades-old phenalenyl chemistry. This review captures such
developments ranging from fundamental understanding to multidirectional
applications of phenalenyl-based radicals.