Synthesis, structural characterisation, and cytotoxicity studies of Bi, W, and Mo containing homo- and hetero-bimetallic polyoxometalates.

Three new and different homo- and hetero-bimetallic polyoxometalate (POM) species have been synthesised by simple one-pot synthetic methods utilising naturally occurring bismite (Bi2O3) (or Bi(NO3)3·5H2O) and aryl sulfonic acids. The POM species isolated are (NH4)14[Bi2W22O76]·14H2O (1·14H2O), (NH4)[Bi(DMSO)7][Mo8O26]·H2O (2·H2O) and [(NH4)4(Mo36O108(OH)4·16H2O)]·45H2O (3·45H2O). The compounds have been characterised by X-ray crystallography, energy dispersive X-ray spectroscopy (EDX), powdered X-ray diffraction (PXRD), mass spectrometry (ESI-MS), Raman spectroscopy, thermogravimetric (TGA) and ICP analyis. In vitro cytoxicity and proliferation studies conducted on 1 and 3, highlight the low toxicity of these species.

2D and 3D Coordination Networks of Polynuclear Bismuth Oxido/Hydroxido Sulfonato Clusters from Low Temperature Solid-State Metathesis Reactions.

Solid-state metathesis (SSM) reactions between Bi(NO3 )3 ⋅5 H2 O and potassium benzene-1,2-disulfonate (=1,2-BDSK2 ), sodium benzene-1,3-disulfonate (=1,3-BDSNa2 ) allows access to the first 2D, {[Bi6 O4 (OH)4 (1-2BDS)2 (NO3 )2 ⋅4 H2 O]⋅11 H2 O}∞ and {[Bi22 O24 (OH)6 (1,3-BDS)6 ⋅12 DMSO]⋅3 DMSO⋅4 H2 O}∞ , and 3D, {[Bi6 O4 (OH)4 (1,3-BDS)3 ⋅4 H2 O]⋅6 H2 O}∞ , polymeric networks of sulfonato encapsulated polynuclear bismuth oxido/hydroxido clusters.

Transformation of Indium and Gallium Metal into Mixed Group†11/13 Ternary Sulfide Nanoparticles by Using a Dithioic Acid.

Heterobimetallic Group 11/13 sulfide nanoparticles (AgInS2 , CuInS2 , Ag9 GaS6 , and CuGaS2 ) are formed by treatment of [M(S2 CAr)3 ] (M=Ga or In) with either AgNO3 or CuCl under mild conditions. The intermediary gallium or indium tris(aryldithioate) complexes are easily prepared by stirring the appropriate metal and aryldithioc acid at room temperature. Overall, this two-step process is a simple solution-based method for transforming Ga and In metal into valuable ternary metallosulfide nanoparticles at relatively low temperatures.

Formation of Group†11 Bismuth Sulfide Nanoparticles Using Bismuth Dithioates under Mild Conditions.

The formation of mixed-metal sulfides with the general structure AgBiS2 and Cu3 BiS2 by a simple two-step process utilizing bismuth dithiocarboxylates as Bi and S precursors is described. A sonochemical reaction of Bi2 O3 with six different aryl dithioic acids: dithiobenzoic acid (BDT-H), 4-methoxydithiobenzoic acid (4-MBDT-H), 3-methyldithiobenzoic acid (3-MBDT-H), 2-mesitylenedithioic acid (2-MDT-H), 4-fluorodithiobenzoic acid (4-FBDT-H), and 2-thiophenedithioic acid (2-TDT-H) resulted in the corresponding complexes: [Bi(BDT)3 ] 1, [Bi(4-MBDT)3 ] 2, [{Bi(3-MBDT)3 }2 ⋅C7 H8 ] (32 ⋅C7 H8 ), [Bi(2-MDT)3 ] 4, [Bi(4-FBDT)3 ] 5 and [Bi(2-TDT)3 ] 6. Microwave irradiation of these bismuth(III)aryldithioate complexes with AgNO3 or CuCl under mild reaction conditions (140 °C) resulted in the respective mixed-metal sulfides. Attempt to synthesize AuBiS2 using similar reaction protocols were unsuccessful, resulting only in the formation of elemental Au0 , S8 and BiOCl.

Polynuclear Bismuth Oxido Sulfonato Clusters, Polymers, and Ion Pairs from Bi2O3 under Mild Conditions.

Eight novel bismuth(III) sulfonato compounds have been synthesized and characterized using the sonochemical reaction of Bi2O3 with a range of sulfonic acids, including 2,5-dimethylbenzenesulfonic acid (2,5-DMSH), 2,4-dinitrobenzenesulfonic acid (2,4-DNSH), 2,5-dichlorobenzenesulfonic acid (2,5-DCSH), 1,2-benzenedisulfonic acid (1,2-BDSH2), 1,3-benzenedisulfonic acid (1,3-BDSH2), 2-sulfobenzoic acid (2-SBH2), 3-sulfobenzoic acid (3-SBH2), and 2-naphthalenesulfonic acid (NPSH). Six of the complexes (1, 2, 4, and 6-8) were structurally characterized through single-crystal X-ray crystallography. In the presence of the monosulfonic acids 2,5-DMSH, 2,4-DNSH, and 2,5-DCSH, polynuclear bismuth(III) oxido clusters were isolated: namely, [Bi6O4(OH)4(2,5-DMS)6(H2O)6]·10H2O (1·10H2O), [Bi6O4(OH)4(2,4-DNS)6(H2O)6]·6H2O (2·6H2O), and [Bi6O4(OH)4(2,5-DCS)6(H2O)6] (3). The disulfonic acid 1,3-BDSH2 also produced an oxido cluster: [Bi6O4(OH)4(1,3-BDS)3]·8H2O (5·8H2O). The remaining diacid ligands (1,2-BDSH2, 2-SBH2, and 3-SBH2), upon reaction with Bi2O3, produced polymeric Bi(III) sulfonato complexes: namely [Bi(1,2-BDS)(OH)(H2O)2]∞ (4), [Bi(2-SB)(2-SBH)H2O]∞·2H2O (6·2H2O), and [NH2(Me)2]2[Bi2(3-SB)4]∞ (7). The larger NPSH ligand produced the monomeric contact ion pair [Bi(NPS)2(H2O)6][NPS]·3H2O (8·3H2O), upon sonication with Bi2O3.

Taking bismuthinite to bismuth sulfide nanorods in two easy steps.

The transformation of mineral bismuthinite, to Bi2S3 nanoparticles, via a simple two-step process is described. The reaction of bismuthinite with two aryldithoic acids gave the complexes; [Bi(S2C(C6H4)-4-CH3)3] and [Bi(S2C(C6H4)-4-OCH3)3]. Mild solution decomposition (120 °C) of these bismuth aryldithioates produced crystalline Bi2S3 nanorods.