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1. Synthesis and Characterization of Cu(II) and Mixed-Valence Cu(I)Cu(II) Clusters Supported by Pyridylamide Ligands

   https://doi.org/10.1021/acs.inorgchem.0c00008  

   Schneider, Joseph D.; Smith, Brett A.; Williams, Grant A.; Powell, Douglas R.; Perez, Felio; Rowe, Gerard T.; Yang, Lei (April 2020, Inorganic Chemistry)
2. Encapsulation of tricopper cluster in a synthetic cryptand enables facile redox processes from Cu ^I Cu ^I Cu ^I to Cu ^II Cu ^II Cu ^II states

   https://doi.org/10.1039/D0SC05441K  

   Zhang, Weiyao; Moore, Curtis E.; Zhang, Shiyu (March 2021, Chemical Science)

   null (Ed.)

   One-pot reaction of tris(2-aminoethyl)amine (TREN), [Cu I (MeCN) 4 ]PF 6 , and paraformaldehyde affords a mixed-valent [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 complex. The macrocyclic azacryptand TREN4 contains four TREN motifs, three of which provide a bowl-shape binding pocket for the [Cu 3 (μ 3 -OH)] 3+ core. The fourth TREN caps on top of the tricopper cluster to form a cryptand, imposing conformational constraints and preventing solvent interaction. Contrasting the limited redox capability of synthetic tricopper complexes reported so far, [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 exhibits several reversible single-electron redox events. The distinct electrochemical behaviors of [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 and its solvent-exposed analog [ TREN3 Cu II Cu II Cu II (μ 3 -O)](PF 6 ) 4 suggest that isolation of tricopper core in a cryptand enables facile electron transfer, allowing potential application of synthetic tricopper complexes as redox catalysts. Indeed, the fully reduced [ TREN4 Cu I Cu I Cu I (μ 3 -OH)](PF 6 ) 2 can reduce O 2 under acidic conditions. The geometric constraints provided by the cryptand are reminiscent of Nature's multicopper oxidases (MCOs). For the first time, a synthetic tricopper cluster was isolated and fully characterized at Cu I Cu I Cu I ( 4a ), Cu II Cu I Cu I ( 4b ), and Cu II Cu II Cu I ( 4c ) states, providing structural and spectroscopic models for many intermediates in MCOs. Fast electron transfer rates (10 5 to 10 6 M −1 s −1 ) were observed for both Cu I Cu I Cu I /Cu II Cu I Cu I and Cu II Cu I Cu I /Cu II Cu II Cu I redox couples, approaching the rapid electron transfer rates of copper sites in MCO. 

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3. Synthesis of conjugated polymers using aryl-bromides via Cu-catalyzed direct arylation polymerization (Cu-DArP)

   https://doi.org/10.1039/c9py01478k  

   Ye, Liwei; Pankow, Robert M.; Schmitt, Alexander; Thompson, Barry C. (December 2019, Polymer Chemistry)

   Initial reports on the novel Cu-catalyzed direct arylation polymerization (Cu-DArP) stated that it required the use of aryl iodides. Herein, we report the first Cu-DArP methodology using more accessible and practical aryl-bromides with catalytic Cu, leading to a range of conjugated polymers with good molecular weights (up to 17.3 kDa) and an undetectable level of defects. 

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4. Metastability and Photoelectrochemical Properties of Cu ₂ SnO ₃ and Cu _2–x Li _x TiO ₃ : Two Cu(I)-Based Oxides with Delafossite Structures

   https://doi.org/10.1021/acs.chemmater.2c03563  

   O’Donnell, Shaun; Kremer, Reinhard K.; Maggard, Paul A. (February 2023, Chemistry of Materials)
5. Heterostructures of Cu _2−x S/Cu _2−x Te plasmonic semiconductors: disappearing and reappearing LSPR with anion exchange

   https://doi.org/10.1039/D2CC01859D  

   Espinosa, Alba Roselia; Novak, Marc; Luo, Qi; Hole, Brandon; Doligon, Clarisse; Prenza Sosa, Kenya; Gray, Jennifer L.; Rossi, Daniel P.; Plass, Katherine E. (August 2022, Chemical Communications)

   Localized surface plasmon resonance (LSPR) of Cu 2− x S nanorods is quenched during the initial Cu 2− x S/Cu 2− x Te core/shell stage of anion exchange then returns as Cu 2− x Te progresses into the nanorod. Phase change within the core accounts for this behaviour illustrating the complexity emergent from anion exchange. 

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