Reversible Scavenging of Dioxygen from Air by a Copper Complex

We report that exposing the dipyrrin complex (^EMindL)Cu(N₂) to air affords rapid, quantitative uptake of O₂ in either solution or the solid-state to yield (^EMindL)Cu(O₂). The air and thermal stability of (^EMindL)Cu(O₂) is unparalleled in molecular copper-dioxygen coordination chemistry, attributable to the ligand flanking groups which preclude the [Cu(O₂)]¹⁺ core from degradation. Despite the apparent stability of (^EMindL)Cu(O₂), dioxygen binding is reversible over multiple cycles with competitive solvent exchange, thermal cycling, and redox manipulations. Additionally, rapid, catalytic oxidation of 1,2-diphenylhydrazine to azoarene with the generation of hydrogen peroxide is observed, through the intermittency of an observable (^EMindL)Cu(H₂O₂) adduct. The design principles gleaned from this study can provide insight for the formation of new materials capable of reversible scavenging of O₂ from air under ambient conditions with low-coordinate Cu^I sorbents.