Designer “Quasi-Benzyne”: The Spontaneous Reduction of Ortho-Diiodotetrafluorobenzene on Water Microdroplets

It has been widely shown that water microdroplets have a plethora of unique properties that are highly distinct from those of bulk water, among which an especially intriguing one is the strong reducing power as a result of the electrons spontaneously generated at the air-water interface. In this study, we take advantage of the reducing power of water microdroplets to reduce ortho-diiodotetrafluorobenzene (o-C₆F₄I₂) into a C₆F₄I₂^•- radical anion. Photoelectron spectroscopy and density functional theory computations reveal that the excess electron in C₆F₄I₂^•- occupies the I-C1-C2-I linkage, which elongates the C-I bonds but surprisingly shortens the C1-C2 bond, making the bond order higher than a double bond, similar to the benzyne molecule, so we named it "quasi-benzyne". The C₆F₄I₂^•- anion was further successfully utilized in a Diels-Alder reaction, a typical reaction for benzyne. This study provides a good example of strategically utilizing the spontaneous properties of water microdroplets and generating an especially exotic anion, and we anticipate that microdroplet chemistry can be an avenue rich in opportunities for new catalyst-free organic reactions.