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

Senevirathna, Dimuthu C.; Werrett, Melissa V.; Blair, Victoria L.; Mehring, M.; Andrews, Philip C.

doi:10.1002/chem.201705981

Cited by 12 publications

(11 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The cluster molecules do not interact with each other through coordinating bonds in the solid state (Figure ). This finding is in contrast to other bismuth oxido sulfonates such as the triflate, benzene‐1,2/1,3‐disulfonates, and 4,8‐disulfonyl‐2,6‐naphthalenedicarboxylates reported recently, which form polymeric networks in the solid state due to bridging sulfonato ligands.…”

Section: Resultscontrasting

confidence: 92%

“…[Bi 9 O 7 (OH)(O 3 SCH=CH 2 ) 11 (dmso) 11 ](O 3 SCH=CH 2 )·3 DMSO (4) crystallizes in the triclinic space group P1 ,i nw hich the asymmetric unit comprises one molecule of cluster 4 ( Figure 5) 6 ], [72] [Bi 6 O 4 (OH) 4 (OTf) 6 (MeCN) 6 ], [49] and other sulfonates. [73] Three of the oxygen atoms are connected to one lateral bismuth atom each, located above the triangularf aces of the octahedron. This structure results in a m 4 -coordination of these oxygen atoms and a[ Bi 6 (m 3 -O) 4 (m 3 -OBi) 3 (m 3 -OH)] 12 + arrangement.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

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

Wrobel

Rüffer

Korb

et al. 2018

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

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).

show abstract

Section: Resultscontrasting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

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

Wrobel

Rüffer

Korb

et al. 2018

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…The so far unknown {Bi 6 O 4 (OH) 4 [OTf] 12 } 6– ([ BOT ] 6– ) cluster hexaanion formally consists of a cationic [Bi 6 (μ 3 -O) 4 (μ 3 -OH) 4 ] 6+ core surrounded by 12 triflate anions. In the core, which is a common motif in hydrolysis products of bismuth salts, − six bismuth(III) centers occupy the corners of an octahedron, whose faces are capped by four oxo and four hydroxo ligands in a μ 3 fashion (the hydroxy protons could not be located crystallographically). The 12 edges of the octahedron are each capped by a triflate anion in a μ 2 -O fashion, six of which form the ring arrangement shown in Figure b.…”

Section: Resultsmentioning

confidence: 99%

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

et al. 2020

View full text Add to dashboard Cite

To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C 6 H 4 - o -CH 2 SCH 3 ) 3 BiCl n ] (3– n )+ ( n = 0–3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative P→Bi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C 6 H 4 - o -CH 2 SCH 3 ) 3 Bi] 3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.

show abstract

“…Compound 6 ([Bi 6 O 4 (OH) 4 (H 2 O) 12 (H 2 DSNDC) 3 ]· x H 2 O) crystallizes in the triclinic space group P 1̅. The three Bi 3+ ions and their symmetry equivalents form the well-known {Bi 6 O 4 (OH) 4 } cluster, which was even observed in two-dimensional and three-dimensional CPs. , The O 2– and OH – ions are disordered and could not be refined separately. Six different linker molecules coordinate to one cluster and connect each of the IBUs to four others.…”

Section: Resultsmentioning

confidence: 99%

“…While the Bi–O clusters and dinuclear IBUs are mostly formed through reactions at room temperature or hydrolysis at moderate temperatures, respectively, the Bi–O chains were mostly obtained by hydrothermal synthesis. A large diversity of reaction methods have been employed to study these compounds, e.g., slow solvent evaporation or diffusion of solvent, hydrolysis, solvothermal and ionothermal reactions, and solid-state metathesis using reaction temperatures between −28 and +180 °C and reaction times of a few minutes up to several days. Unfortunately, only very few systematic multiparameter studies on the product formation have been reported today; hence, bismuth CPs seem to be perfectly suited for these investigations.…”

Section: Introductionmentioning

confidence: 99%

Multiparameter High-Throughput and in Situ X-ray Diffraction Study of Six New Bismuth Sulfonatocarboxylates: Discovery, Phase Transformation, and Reaction Trends

Albat

Stock

2018

Inorg. Chem.

View full text Add to dashboard Cite

With the employment of high-throughput methods, the system Bi/4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (HDSNDC)/HO/additive (HNO or NaOH) was systematically investigated under hydrothermal reaction conditions. The influence of the molar ratio of the starting materials, pH, and reaction temperature and time was investigated in more than 500 reactions. The product formation is highly sensitive toward small changes of the synthesis parameters, but six new bismuth sulfonatocarboxylates were reproducibly obtained starting from clear solutions of the reactants. All compounds were structurally characterized from single-crystal X-ray diffraction data. Fully deprotonated linker ions are found in [BiO(OH)(HO)(DSNDC)] (1), [Bi(OH)(DSNDC)] (2), [BiO(OH)(HO)(DSNDC)] (3), and [BiO(OH)(HO)(DSNDC)]·4HO (4), while the presence of larger amounts of acid or short reaction times leads to compounds with noncoordinating -COOH groups, [Bi(OH)(HO)(DSNDC)(HDSNDC)] (5) and [BiO(OH)(HO)(HDSNDC)]· xHO (6), respectively. The inorganic building units (IBUs) in all six structures differ substantially from each other; the IBUs found in 2 ({Bi(OH)}), 5 (BiO polyhedron), and 6 ({BiO(OH)} cluster) have been reported in the literature, while new IBUs are observed for 1 (chains of composition {BiO(OH)}), 3 ({BiO(OH)} cluster), and 4 ({BiO(OH)} cluster). Systematic variation of the reaction temperature and time indicated their distinct influence on product formation. Hence, in situ powder X-ray diffraction measurements at Deutsches Elektronen-Synchrotron, Hamburg, Germany, employing synchrotron radiation were carried out. In all studied in situ reactions, compound 6 is first observed and subsequently transformed to 1, 2, 4, and 5, depending on the reaction time and temperature as well as concentration of the starting materials.

show abstract

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

Cited by 12 publications

References 26 publications

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

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

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

Multiparameter High-Throughput and in Situ X-ray Diffraction Study of Six New Bismuth Sulfonatocarboxylates: Discovery, Phase Transformation, and Reaction Trends

Contact Info

Product

Resources

About