Hydrolysis of a Basic Bismuth Nitrate-Formation and Stability of Novel Bismuth Oxido Clusters

The synthesis of the nanoscaled bismuth oxido clusters [Bi38O45(NO3)(20)(DMSO)(28)](NO3)(4)center dot 4DMSO (1a) and [Bi38O45(OH)(2)(pTsO)(8)(NO3)(12)(DMSO)(24)] (NO3)(2)center dot 4DMSO center dot 2H(2)O (2) starting from the basic bismuth nitrate [Bi6O4(OH)(4)](NO3)(6)center dot H2O is reported herein. Single-crystal X-ray diffraction analysis, ESI mass spectrometry, thermogravimetric analysis, and molecular dynamics simulation were used to study the formation, structure, and stability of these large metal oxido clusters. Compounds 1a and 2 are based on a [Bi38O45](24+) core, which is structurally related to delta-Bi2O3. Examination of the fragmentation pathways of 1a and 2 by infrared multi-photon dissociation (IRMPD) tandem MS experiments allows the identification of novel bismuth oxido cluster species in the gas phase.