Abstract
The copper hydride nanocluster (NC) [Cu29Cl4H22(Ph2phen)12]Cl (2; Ph2phen = 4,7-diphenyl-1,10-phenanthroline) was isolated cleanly, and in good yields, by controlled growth from the smaller NC, [Cu25H22(PPh3)12]Cl (1), in the presence of Ph2phen and a chloride source at room temperature. Complex 2 was fully characterized by single-crystal X-ray diffraction, XANES, and XPS, and represents a rare example of an N∗ = 2 superatom. Its formation from 1 demonstrates that atomically precise copper clusters can be used as templates to generate larger NCs that retain the fundamental electronic and bonding properties of the original cluster. A time-resolved kinetic evaluation of the formation of 2 reveals that the mechanism of cluster growth is initiated by rapid ligand exchange. The slower extrusion of CuCl monomer, its transport, and subsequent capture by intact clusters resemble elementary steps in the reactant-assisted Ostwald ripening of metal nanoparticles.
| Original language | English |
|---|---|
| Pages (from-to) | 8385-8390 |
| Number of pages | 6 |
| Journal | Chemistry of Materials |
| Volume | 28 |
| Issue number | 22 |
| DOIs | |
| State | Published - Nov 22 2016 |
| Externally published | Yes |
Funding
This work was supported by the Center for Sustainable Use of Renewable Feedstocks (CenSURF), a National Science Foundation (NSF) Center for Chemical Innovation (CCI). Financial support of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under the Catalysis Science Initiative (DE-FG-02-03ER15467), and the NSF PIRE program (OISE-0968399), is also gratefully acknowledged. NMR spectra were collected on an instrument supported by an NIH Shared Instrumentation Grant (SIG, 1S10OD012077-01A1). ESI mass spectra and XPS data were acquired at the MRL Shared Experimental Facilities, supported by the MRSEC Program of the NSF under Award DMR 1121053 and a member of the NSF-funded Materials Research Facilities Network. The X-ray absorption spectroscopy studies were conducted on beamline 4-1, at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Stanford University.