From {Bi22O26} to chiral ligand-protected {Bi38O45}-based bismuth oxido clusters.

The reaction of [Bi(22)O(26)(OSiMe(2)tBu)(14)] (1) in THF with salicylic acid gave [Bi(22)O(24)(HSal)(14)] (2) first, which was converted into [Bi(38)O(45)(HSal)(22)(OH)(2)(DMSO)(16.5)]·DMSO·H(2)O (3·DMSO·H(2)O) after dissolution and crystallization from DMSO. Single-crystal X-ray diffraction analysis and ESI mass spectrometry associated with infrared multi-photon dissociation (IRMPD) tandem MS experiments confirm the formation of the large and quite stable bismuth oxido cluster 3.

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).

Organic-inorganic hybrid materials starting from the novel nanoscaled bismuth oxido methacrylate cluster [Bi38O45(OMc)24(DMSO)9]·2DMSO·7H2O.

The reaction of the basic bismuth nitrate [Bi(6)O(4)(OH)(4)](NO(3))(6)·H(2)O with sodium methacrylate in DMSO gave [Bi(38)O(45)(OMc)(24)(DMSO)(9)]·2DMSO·7H(2)O (OMc = O(2)CC(3)H(5)), which is highly soluble in organic solvents. By copolymerization of the bismuth oxido cluster with methyl methacrylate transparent, radiopaque organic-inorganic hybrid materials were obtained.