Open AccessReversible Scavenging of Dioxygen from Air by a Copper Complex
Author(s) -
Kurtis M. Carsch,
Andrei Iliescu,
Ryan D. McGillicuddy,
Jarad A. Mason,
Theodore A. Betley
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c10254
Subject(s) - chemistry , copper , hydrogen peroxide , adduct , scavenging , transition metal dioxygen complex , ligand (biochemistry) , catalysis , redox , oxygen , yield (engineering) , photochemistry , inorganic chemistry , organic chemistry , antioxidant , biochemistry , materials science , receptor , metallurgy
We report that exposing the dipyrrin complex ( EMind L)Cu(N 2 ) to air affords rapid, quantitative uptake of O 2 in either solution or the solid-state to yield ( EMind L)Cu(O 2 ). The air and thermal stability of ( EMind L)Cu(O 2 ) is unparalleled in molecular copper-dioxygen coordination chemistry, attributable to the ligand flanking groups which preclude the [Cu(O 2 )] 1+ core from degradation. Despite the apparent stability of ( EMind L)Cu(O 2 ), 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 ( EMind L)Cu(H 2 O 2 ) adduct. The design principles gleaned from this study can provide insight for the formation of new materials capable of reversible scavenging of O 2 from air under ambient conditions with low-coordinate Cu I sorbents.