Homo‐ and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates

Abstract

The synthesis and characterization of six homo- and heteroleptic coordination polymers and oxido clusters of bismuth(III) vinylsulfonates are reported. The solvent-mediated reaction of BiPh and vinylsulfonic acid in ethanol produces [{Ph Bi(O SCH=CH )} ] (1), which crystallizes as a one-dimensional coordination polymer as a result of bridging sulfonato ligands accompanied by intermolecular Bi⋅⋅⋅ π(arene) London dispersion interactions. In solution, compound 1 equilibrates to give [{PhBi(O SCH=CH ) } ] (2) and BiPh . Compound 2 is obtained as a single product by the reaction of BiPh with vinylsulfonic acid in acetonitrile and crystallizes as a one-dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O SCH=CH ) } ] (3) was isolated as a two-dimensional coordination polymer, which is quite moisture sensitive, but did not provide a distinct polynuclear bismuth oxido cluster upon hydrolysis. However, by treatment of [Bi O (OH) (NO ) ]⋅H O or [Bi O (OMc) (dmso) (H O) ]⋅2 DMSO⋅5 H O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi O (OH)(O SCH=CH ) (dmso) ](O SCH=CH )⋅3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi O (NO ) (O SCH=CH ) (dmso) ](O SCH=CH ) ⋅2 DMSO (5), was observed as a co-crystallizing side product, which upon further hydrolysis afforded [Bi O (NO ) (OH) (O SCH=CH ) (dmso) (H O) ](O SCH=CH ) ⋅2 H O (6).

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces

“…The main reflection corresponds to the interlayer distance, assuming a closed, packed nanocluster arrangement [ 20 , 50 ]. Thus, an interlayer distance for 2 of 1.975 nm (2 θ = 4.47°) was calculated using Bragg’s equation.…”

“…These so-called bismuth subnitrates were recently studied in order to elucidate the molecular mechanisms of the condensation that lead to the formation of bismuth oxido nitrates with up to 38 bismuth atoms, e.g., in the nanoscaled [Bi 38 O 45 (NO 3 ) 24 ], using a combined in situ small-angle X-ray scattering (SAXS) and pair distribution function (PDF) analysis approach, as well as electrospray ionization mass spectrometry (ESI-MS) [ 16 , 17 , 18 ]. The Bi 38 O 45 core seems to be the most stable one among the bismuth oxido clusters, and various molecules of this type were reported recently, including sulfonates, salicylates, nitrates, and methacrylates [ 13 , 14 , 19 , 20 , 21 , 22 , 23 , 24 ]. However, most of them suffer from either low hydrolytic stability at the ligand periphery, low solubility, low biocompatibility of their ligands, or accessibility on a large scale.…”

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…The trans angles in the equatorial ОBiO plane are 177. The synthesis and characteristics of two coordination polymers of vinylbismuth(III) sulfonates were reported [64]. The bismuth complexes were synthesized from triphenylbismuth and vinylsulfonic acid in ethanol or acetonitrile (Scheme 55).…”

Heavy Metals Make a Chain: A Catenated Bismuth Compound

“…An umber of other authors have invokeds imilar arguments to explain unusualg eometries found in avariety of other bismuth compounds. [20][21][22] The only reasonablyc lose interaction that the bismuth centreo f2a does make is with disordered H20B/F at ad istance of 3. The formation of such ac ontactd oes support the presence of as tereochemically activel one pair on bismuth.…”