Phenalenyl Radical: Smallest Polycyclic Odd Alternant Hydrocarbon Present in the Graphene Sheet.

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.