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

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 3 and vinylsulfonic acid in ethanol produces [{Ph 2 Bi(O 3 SCH=CH 2 )} n ] ( 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 3 SCH=CH 2 ) 2 } n ] ( 2 ) and BiPh 3 . Compound 2 is obtained as a single product by the reaction of BiPh 3 with vinylsulfonic acid in acetonitrile and crystallizes as a one‐dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O 3 SCH=CH 2 ) 3 } n ] ( 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 6 O 4 (OH) 4 (NO 3 ) 6 ]⋅H 2 O or [Bi 38 O 45 (OMc) 24 (dmso) 9 (H 2 O) 2 ]⋅2 DMSO⋅5 H 2 O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi 9 O 7 (OH)(O 3 SCH=CH 2 ) 11 (dmso) 11 ](O 3 SCH=CH 2 )⋅3 DMSO ( 4 ), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi 38 O 45 (NO 3 ) 8 (O 3 SCH=CH 2 ) 14 (dmso) 18 ](O 3 SCH=CH 2 ) 2 ⋅2 DMSO ( 5 ), was observed as a co‐crystallizing side product, which upon further hydrolysis afforded [Bi 38 O 45 (NO 3 ) 6 (OH) 4 (O 3 SCH=CH 2 ) 12 (dmso) 23 (H 2 O) 2 ](O 3 SCH=CH 2 ) 2 ⋅2 H 2 O ( 6 ).