title: Orbital phase design of diradicals.
abstract: Over the last three decades the rational design of diradicals has been a challenging issue because of their special features and activities in organic reactions and biological processes. The orbital phase theory has been developed for understanding the properties of diradicals and designing new candidates for synthesis. The orbital phase is an important factor in promoting the cyclic orbital interaction. When all of the conditions: (1) the electron-donating orbitals are out of phase; (2) the accepting orbitals are in phase; and (3) the donating and accepting orbitals are in phase, are simultaneously satisfied, the system is stabilized by the effective delocalization and polarization. Otherwise, the system is less stable. According to the orbital phase continuity requirement, we can predict the spin preference of π-conjugated diradicals and relative stabilities of constitutional isomers. Effects of the intramolecular interaction of bonds and unpaired electrons on the spin preference, thermodynamic and kinetic stabilities of the singlet and triplet states of localized 1,3-diradicals were also investigated by orbital phase theory. Taking advantage of the ring strains, several monocyclic and bicyclic systems were designed with appreciable singlet preference and kinetic stabilities. Substitution effects on the ground state spin and relative stabilities of diradicals were rationalized by orbital interactions without loss of generality. Orbital phase predictions were supported by available experimental observations and sophisticated calculation results. In comparison with other topological models, the orbital phase theory has some advantages. Orbital phase theory can provide a general model for both π-conjugated and localized diradicals. The relative stabilities and spin preference of all kinds of diradicals can be uniformly rationalized by the orbital phase property. The orbital phase theory is applied to the conformations of diradicals and the geometry-dependent behaviors. The insights gained from the orbital phase theory are useful in a rational design of stable 1,3-diradicals.
authors.affiliation: Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, People's Republic of China, majing@nju.edu.cn.
authors.forename: Jing
authors.initials: J
authors.lastname: Ma
authors.forename: Satoshi
authors.initials: S
authors.lastname: Inagaki
authors.forename: Yong
authors.initials: Y
authors.lastname: Wang
mesh_terms: D004583:Electrons; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013816:Thermodynamics