Hydrolysis of a basic bismuth nitrate--formation and stability of novel bismuth oxido clusters

The synthesis of the nanoscaled bismuth oxido clusters Bi(38)O(45)(NO(3))(20)(DMSO)(28)](NO(3))(4)·4DMSO (1a) and Bi(38)O(45)(OH)(2)(pTsO)(8)(NO(3))(12)(DMSO)(24)](NO(3))(2)·4DMSO·2H(2)O (2) starting from the basic bismuth nitrate Bi(6)O(4)(OH)(4)](NO(3))(6)·H(2)O 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 Bi(38)O(45)](24+) core, which is structurally related to δ-Bi(2)O(3). 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.