The enzyme tyrosinase contains a reactive side‐on peroxo dicopper(II) center as catalytically active species in C−H oxygenation reactions. The tyrosinase activity of the isomeric bis(μ‐oxo) dicopper(III) form has been discussed controversially. The synthesis of bis(μ‐oxo) dicopper(III) species [Cu2(μ‐O)2(L1)2](X)2 ([O1](X)2, X=PF6−, BF4−, OTf−, ClO4−), stabilized by the new hybrid guanidine ligand 2‐{2‐((dimethylamino)methyl)phenyl}‐1,1,3,3‐tetramethylguanidine (L1), and its characterization by UV/Vis, Raman, and XAS spectroscopy, as well as cryo‐UHR‐ESI mass spectrometry, is described. We highlight selective oxygenation of a plethora of phenolic substrates mediated by [O1](PF6)2, which results in mono‐ and bicyclic quinones and provides an attractive strategy for designing new phenazines. The selectivity is predicted by using the Fukui function, which is hereby introduced into tyrosinase model chemistry. Our bioinspired catalysis harnesses molecular dioxygen for organic transformations and achieves a substrate diversity reaching far beyond the scope of the enzyme.
Fully inorganic, colloidal gold nanoclusters (NCs) constitute a new class of nanomaterials that are clearly distinguishable from their commonly studied metal–organic ligand‐capped counterparts. As their synthesis by chemical methods is challenging, details about their optical properties remain widely unknown. In this work, laser fragmentation in liquids is performed to produce fully inorganic and size‐controlled colloidal gold NCs with monomodal particle size distributions and an fcc‐like structure. Results reveal that these NCs exhibit highly pronounced photoluminescence with quantum yields of 2%. The emission behavior of small (2–2.5 nm) and ultrasmall (<1 nm) NCs is significantly different and dominated by either core‐ or surface‐based emission states. It is further verified that emission intensities are a function of the surface charge density, which is easily controllable by the pH of the surrounding medium. This experimentally observed correlation between surface charge and photoluminescence emission intensity is confirmed by density functional theoretical simulations, demonstrating that fully inorganic NCs provide an appropriate material to bridge the gap between experimental and computational studies of NCs. The presented study deepens the understanding of electronic structures in fully inorganic colloidal gold NCs and how to systematically tune their optical properties via surface charge density and particle size.
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