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J Am Chem Soc. 2015 Oct 21;137(41):13319-24. doi: 10.1021/jacs.5b07574. Epub 2015 Oct 13.

A Cu25 Nanocluster with Partial Cu(0) Character.

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Department of Chemistry & Biochemistry, and ‡Department of Chemical Engineering, University of California , Santa Barbara, California 93106, United States.


Atomically precise copper nanoclusters (NCs) are of immense interest for a variety of applications, but have remained elusive. Herein, we report the isolation of a copper NC, [Cu25H22(PPh3)12]Cl (1), from the reaction of Cu(OAc) and CuCl with Ph2SiH2, in the presence of PPh3. Complex 1 has been fully characterized, including analysis by X-ray crystallography, XANES, and XPS. In the solid state, complex 1 is constructed around a Cu13 centered-icosahedron and formally features partial Cu(0) character. XANES of 1 reveals a Cu K-edge at 8979.6 eV, intermediate between the edge energies of Cu(0) and Cu(I), confirming our oxidation state assignment. This assignment is further corroborated by determination of the Auger parameter for 1, which also falls between those recorded for Cu(0) and Cu(I).

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