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

The final publication is available at https://doi.org/10.1515/pac-2023-0114
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 y0. 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.