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

Abstract The synthesis of the nanoscaled bismuth oxido clusters [Bi 38 O 45 ‐ (NO 3 ) 20 (DMSO) 28 ](NO 3 ) 4 ⋅4 DMSO ( 1 a ) and [Bi 38 O 45 (OH) 2 ( p TsO) 8 ‐ (NO 3 ) 12 (DMSO) 24 ](NO 3 ) 2 ⋅4 DMSO⋅ 2 H 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 1 a 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 1 a and 2 by infrared multi‐photon dissociation (IRMPD) tandem MS experiments allows the identification of novel bismuth oxido cluster species in the gas phase.