Far-infrared absorption spectra of synthetically-prepared, ligated metal clusters with Au6, Au8, Au9 and Au6Pd metal cores
Alvino, Jason F
Adnan, Rohul H
Golovko, Vladimir B
Metha, Gregory F
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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.
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