Closed-shell and open-shell dual nature of singlet diradical compounds

Abstract

Abstract Unlike triplet diradicals, singlet diradicals can vary in diradical character from 0 % to 100 % depending on linker units that allow two formally unpaired electrons to couple covalently. In principle, the electronic structure of singlet diradicals can be described as a quantum superposition of closed-shell and open-shell structures. This means that, depending on the external environment, singlet diradicals can behave as either closed-shell or open-shell species. This paper summarizes our progress in understanding the electronic structure of π-conjugated singlet diradical molecules in terms of closed-shell and open-shell dual nature. We first discuss the coexistence of intra- and intermolecular covalent bonding interactions in the π-dimer of a singlet diradical molecule. The intra- and intermolecular coupling of two formally unpaired electrons are related to closed-shell and open-shell nature of singlet diradical, respectively. Then we demonstrate the coexistence of the covalent bonding interactions in the one-dimensional stack of singlet diradical molecules having different diradical character. The relative strength of the interactions is varied with the magnitude of singlet diradical index y 0. Finally, we show the dual reactivity of a singlet diradical molecule, which undergoes rapid [4 + 2] and [4 + 4] cycloaddition reactions in the dark at room temperature. Closed-shell and open-shell nature endow the singlet diradical molecule with the reaction manner as diene and diradical species, respectively.