We report the first infrared spectra of multiply-charged anions in the gas phase. The spectra of SO42(H2O)n, with n=324, show four main bands assigned to two vibrations of the dianionic core, the water bending mode, and solvent libration. The triply degenerate SO42 antisymmetric stretch vibration probes the local solvent symmetry, while the solvent librational band is sensitive to the hydrogen bonding network. The spectra and accompanying electronic structure calculations indicate a highly symmetric structure for the n=6 cluster and closure of the first solvation shell at n=12.

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