Two novel nanoscaled bismuth oxido clusters, [Bi38O45(OMc)22(C8H7SO3)2(DMSO)6(H2O)1.5]·2.5H2O and [Bi38O45(HSal)22(OMc)2(DMSO)15(H2O)]·DMSO·2H2O

Abstract

The synthesis of [Bi 38 O 45 (OMc) 22 (C 8 H 7 SO 3 ) 2 (DMSO) 6 (H 2 O) 1.5 ] · 2.5H 2 O ( 1 ·2.5H 2 O) (OMc-methacrylate) and [Bi 38 O 45 (HSal) 22 (OMc) 2 (DMSO) 15 (H 2 O)] · DMSO·2H 2 O ( 2 · DMSO·2H 2 O) (Hsal-salicylate) starting from [Bi 38 O 45 (OMc) 24 (DMSO) 9 ]·2DMSO·7H 2 O and sodium 4-vinylbenzenesulfonate and salicylic acid, respectively, is presented. The bismuth oxido clusters show diameters of 2.9 nm ( 1 ) and 2.4 nm ( 2 ) and molecular weights of 11,440.22 g/mol ( 1 ·2.5H 2 O) and 13,151.92 g/mol ( 2 · DMSO·2H 2 O). The polynuclear framework of 1 and 2 is quite similar; nevertheless, a comparison of the bismuth and oxygen atom positions of 1 and 2 shows a weighted root mean square deviation of 0.307 and 0.413 Å , respectively, as a result of the different coordination sphere. Both [Bi 38 O 45 ] 24 + cores in 1 and 2 are coordinated by two different anionic ligands with a ligandto-ligand ratio of 22:2, which might indicate two particularly reactive positions at each bismuth oxido cluster.

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

“…The products of the hydrolysis of bismuth nitrate and perchlorate have been studied crystallographically and show the formation of discrete oxido cluster species. ,,− Complexes with salicylate (H 2 sal = HO-2-C 6 H 4 CO 2 H) were particularly of interest owing to the known biological activity of bismuth subsalicylate. Among the nuclearities observed for that ligand alone are [Bi 4 (μ 3 -O) 2 (Hsal) 8 ]·2Solv (Solv = MeCN or MeNO 2 ), [Bi 9 O 7 (Hsal) 13 (Me 2 CO) 1.5 ]·(Me 2 CO) 1.5 , [Bi 22 O 24 (Hsal) 14 ], , [Bi 38 O 45 (Hsal) 22 (OH) 2 (DMSO) 16.5 ]·DMSO-·H 2 O, , and [Bi 38 O 44 (Hsal) 26 (Me 2 CO) 16 (H 2 O) 2 ]·(Me 2 CO) 4 . ,, Oxido-clusters supported by alkoxides, other carboxylates, and hexafluoroacetylacetonate have also been reported. ,,,− They contain a core composed of Bi­(III) and oxygen atoms that has an overall positive charge. These cores are then surrounded by negatively charged carboxylate ligands to form an overall neutral compound.…”

Synthesis and structural studies of the simplest bismuth(iii) oxo-salicylate complex: [Bi4(μ3-O)2(HO-2-C6H4CO2)8]·2Solv (Solv = MeCN or MeNO2)

“…The chemistry of these oxo clusters has been reviewed. 9,[11][12][13][14][15][16][17] Often when reacting bismuth halides with sodium salts of alkoxides or carboxylates, oxo-compounds are obtained. We discovered that protonolysis of BiPh 3 using acidic organic compounds can avoid the formation of oxo ligands and have applied this methodology to the production of [Bi(OC 6 F 5 ) 3 (toluene)] 2 , Bi(Hsal) 3 and various derivatives thereof.…”

Real-Time Observation of “Soft” Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate

“…Metallodrugs have been used therapeutically since antiquity. , Those based upon bismuth suboxides are known for their antibacterial and antiviral properties, , with bismuth subsalicylate (Pepto-Bismol) used to treat infection by Helicobacter pylori and ranitidine bismuth citrate shown to inhibit COVID-19 replication . Despite this history, the structures of many Bi metallodrugs are unknown, due to the rich hydrolysis chemistry of bismuth, which forms poorly characterized colloids, with multiple cluster sizes. − …”