Abstract
Rational design and synthesis of catalytically active two-dimensional (2D) materials with an abundance of atomically precise active sites in their basal planes remains a great challenge. Here, we report a ligand exchange strategy to exfoliate bulk [Cu
4
(OH)
6
][O
3
S(CH
2
)
4
SO
3
] cuprate crystals into atomically thin 2D cuprate layers ([Cu
2
(OH)
3
]
+
). The basal plane of 2D cuprate layers contains periodic arrays of accessible unsaturated Cu(II) single sites (2D-CuSSs), which are found to promote efficient oxidative Chan-Lam coupling. Our mechanistic studies reveal that the reactions proceed via coordinatively unsaturated CuO
4
(II) single sites with the formation of Cu(I) species in the rate-limiting step, as corroborated by both operando experimental and theoretical studies. The robust stability of 2D-CuSSs in both batch and continuous flow reactions, coupled with their recyclability and good performance in complex molecule derivatization, render 2D-CuSSs attractive catalyst candidates for broad utility in fine chemical synthesis.
A ligand exchange strategy exfoliates bulk cuprate crystals into atomically thin 2D cuprate layers with periodic unsaturated copper single sites, which are found to promote efficient oxidative Chan-Lam coupling.