Royal Society of Chemistry, RSC Advances, 44(3), p. 22140
DOI: 10.1039/c3ra44803g
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The far infra-red absorption spectra of a series of chemically synthesised, atomically precise phosphine-stabilised gold cluster compounds have been recorded using synchrotron light for the first time. Far-IR spectra of the Au6(Ph2P(CH2)3PPh2)4(NO3)2, Au8(PPh3)8(NO3)2, Au9(PPh3)8(NO3)3, and Pd(PPh3)Au6(PPh3)6(NO3)2 clusters reveal a complex series of peaks between 80 and 475 cm−1, for which all significant peaks can be unambiguously assigned by comparison with Density Functional Theory (DFT) geometry optimisations and frequency calculation. Strong absorptions in all spectra near 420 cm−1 are assigned to the P-Ph3 stretching vibrations. Distinct peaks within the spectrum of each specific cluster are assigned to the cluster core vibrations: 80.4 and 84.1 cm−1 (Au6) 165.1 and 166.4 cm−1 (Au8), 170.1 and 185.2 cm−1 (Au9), and 158.9, 195.2, and 206.7 cm−1 (Au6Pd). The positions of these peaks are similar to those observed to occur for the neutral Au7 cluster in the gas phase (Science, 2008, 321, 674-676). Au-P stretching vibrations only occur for Au6 near 420 cm−1, although they appear near 180 cm−1 for Au6Pd and involve gold core vibrations.