The Hybrid Organic‐Inorganic 2‐D Material (CsNa2[{Sn(CH3)2}3(H2O)4(β‐XW9O33)]·7H2O)∞ (X = AsIII, SbIII) and Its Solution Properties

Hussain, Firasat; Reicke, Markus; Kortz, Ulrich

doi:10.1002/ejic.200400059

Cited by 62 publications

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“…In addition to the results we have already published (see ref. [18]) and the structure presented herein, we have several other discrete and also polymeric polyanion structures with completely unprecedented geometries. These results will be published elsewhere.…”

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confidence: 93%

“…We have already demonstrated that this electrophile can be incorporated in lone-pair-containing polyanion precursors. [18] Furthermore, we have discovered that the two organic groups are always trans to each other, which allows the construction of large polyanions with unexpected geometries. Herein we report the reactivity of dimethyltindichloride with the trilacunary Keggin precursors [A-XW 9 O 34 ] 9À (X = P, As).…”

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confidence: 99%

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The Ball‐Shaped Heteropolytungstates [{Sn(CH₃)₂(H₂O)}₂₄{Sn(CH₃)₂}₁₂(A‐XW₉O₃₄)₁₂]³⁶⁻

2005

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Polyoxometalates can be considered as soluble metal-oxide fragments with an enormous structural variety and a multitude of interesting properties. [1][2][3][4][5][6] The first polyanions were reported almost two centuries ago. [7, 8] Nevertheless, interest in this class of compounds is larger than ever before. The search for novel polyanions is predominantly driven by the catalytic properties of many transition-metal-substituted polyoxotungstates, [9] and by potential applications in bioand nanotechnology.Besides being useful, the symmetry and molecular nature of polyoxometalates are highly attractive features. . [16] Recently we also reported on large polyoxotungstates based on titanium(iv). [17] It is important to realize that the mechanism of formation of polyoxometalates is still not well understood and commonly described as self-assembly. Therefore it is usually not possible to design a multi-step sequence for the synthesis of a novel polyoxometalate. As a result the design of novel polyoxometalates remains a challenge.In our search for a cationic linker which is hydrolytically stable and allows for covalent attachment of organic functional groups we identified the diorganotin group (R 2 Sn 2+ , R = CH 3 , C 6 H 5 etc.) as an interesting candidate. We have already demonstrated that this electrophile can be incorporated in lone-pair-containing polyanion precursors.[18] Furthermore, we have discovered that the two organic groups are always trans to each other, which allows the construction of large polyanions with unexpected geometries. Herein we report the reactivity of dimethyltindichloride with the trilacunary Keggin precursors [A-XW 9 O 34 ] 9À (X = P, As). Interaction of (CH 3 ) 2 SnCl 2 with Na 9 [A-PW 9 O 34 ] in the ratio 3:1 in aqueous medium (pH 4) resulted in the dodecameric, ball-shaped anion [{Sn(CH 3 ) 2 (H 2 O)} 24 {Sn(CH 3 ) 2 } 12 (A-PW 9 O 34 ) 12 ] 36À (1; Figure 1 and Figure 2). We were also able to prepare the isostructural arsenic analogue [{Sn(CH 3 ) 2 -(H 2 O)} 24 {Sn(CH 3 ) 2 } 12 (A-AsW 9 O 34 ) 12 ] 36À (2) by an identical procedure. Both compounds crystallized as mixed cesiumsodium salts and are in fact isomorphous. [19] Owing to the high symmetry of the solid state arrangement (space group Im3 ), the asymmetric unit of 1 and 2 is very small and includes only five tungsten and two tin atoms (Figure 1). The spherical structure of 1 and 2 is spectacular in terms of geometry and size (diameter of % 30 ) and is unprecedented in polyoxotungstate chemistry (Figure 2 and Figure 3). This supermolecular assembly is composed of 12 trilacunary [A-XW 9 O 34 ] 9À (X = P, As) Keggin fragments which are linked by a total of 36 dimethyltin groups (12 inner (CH 3 ) 2 Sn 2+ and 24 outer (CH 3 ) 2 (H 2 O)Sn 2+ groups) resulting in a polyanion with T h symmetry. Note that 1 and 2 have almost 1000 atoms and a

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The Ball‐Shaped Heteropolytungstates [{Sn(CH₃)₂(H₂O)}₂₄{Sn(CH₃)₂}₁₂(A‐XW₉O₃₄)₁₂]³⁶⁻

2005

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“…The choice of the dual combination, electrophilic linker/nucleophilic POM unit, represents a key parameter for the targeted geometry of the resulting assembly. The control of the design can be achieved using an electrophilic linker with reduced coordinative requirement as exemplified by Kortz et al using the dimethyltin cation {SnMe 2 } 2+ where four equatorial coordination sites are available [45][46][47][48][49]. The length of the linker can be increased, for example by using the dinuclear unit {Mo 2 O 2 S 2 } 2+ , which permits to enlarge the size of the resulting modular species [50].…”

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Control of the modularity of {Mo2O2S2}-containing polyoxometalates. Synthesis, structure and characterization of tri- and tetra-modular assemblies based on the [β-B-AsW9O33]9− anion

Pilette

Marrot

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et al. 2010

Inorganica Chimica Acta

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“…1c) must have happened. Such isomerization phenomenon has been observed in previous research of TAs [2,[27][28][29].…”

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Synthesis, structure and electrochemical properties of a Fe III –Ce III heterometallic sandwich-type tungstoantimonate with novel 2-D infinite structure [Ce(H 2 O) 8 ][Ce(H 2 O) 6 ][Fe 4 (H 2 O) 10 (B-β-SbW 9 O 33 ) 2 ]·16H 2 O

Song

Gong

et al. 2015

Inorganic Chemistry Communications

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The Hybrid Organic‐Inorganic 2‐D Material (CsNa₂[{Sn(CH₃)₂}₃(H₂O)₄(β‐XW₉O₃₃)]·7H₂O)_∞ (X = As^III, Sb^III) and Its Solution Properties

Abstract: We report on the hybrid organic-inorganic 2-D materials (

Cited by 62 publications

References 27 publications

The Ball‐Shaped Heteropolytungstates [{Sn(CH₃)₂(H₂O)}₂₄{Sn(CH₃)₂}₁₂(A‐XW₉O₃₄)₁₂]³⁶⁻

The Ball‐Shaped Heteropolytungstates [{Sn(CH₃)₂(H₂O)}₂₄{Sn(CH₃)₂}₁₂(A‐XW₉O₃₄)₁₂]³⁶⁻

Control of the modularity of {Mo2O2S2}-containing polyoxometalates. Synthesis, structure and characterization of tri- and tetra-modular assemblies based on the [β-B-AsW9O33]9− anion

Synthesis, structure and electrochemical properties of a Fe III –Ce III heterometallic sandwich-type tungstoantimonate with novel 2-D infinite structure [Ce(H 2 O) 8 ][Ce(H 2 O) 6 ][Fe 4 (H 2 O) 10 (B-β-SbW 9 O 33 ) 2 ]·16H 2 O

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The Hybrid Organic‐Inorganic 2‐D Material (CsNa2[{Sn(CH3)2}3(H2O)4(β‐XW9O33)]·7H2O)∞ (X = AsIII, SbIII) and Its Solution Properties

Abstract: We report on the hybrid organic-inorganic 2-D materials (

Cited by 62 publications

References 27 publications

The Ball‐Shaped Heteropolytungstates [{Sn(CH3)2(H2O)}24{Sn(CH3)2}12(A‐XW9O34)12]36−

The Ball‐Shaped Heteropolytungstates [{Sn(CH3)2(H2O)}24{Sn(CH3)2}12(A‐XW9O34)12]36−

Control of the modularity of {Mo2O2S2}-containing polyoxometalates. Synthesis, structure and characterization of tri- and tetra-modular assemblies based on the [β-B-AsW9O33]9− anion

Synthesis, structure and electrochemical properties of a Fe III –Ce III heterometallic sandwich-type tungstoantimonate with novel 2-D infinite structure [Ce(H 2 O) 8 ][Ce(H 2 O) 6 ][Fe 4 (H 2 O) 10 (B-β-SbW 9 O 33 ) 2 ]·16H 2 O

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The Hybrid Organic‐Inorganic 2‐D Material (CsNa₂[{Sn(CH₃)₂}₃(H₂O)₄(β‐XW₉O₃₃)]·7H₂O)_∞ (X = As^III, Sb^III) and Its Solution Properties

The Ball‐Shaped Heteropolytungstates [{Sn(CH₃)₂(H₂O)}₂₄{Sn(CH₃)₂}₁₂(A‐XW₉O₃₄)₁₂]³⁶⁻

The Ball‐Shaped Heteropolytungstates [{Sn(CH₃)₂(H₂O)}₂₄{Sn(CH₃)₂}₁₂(A‐XW₉O₃₄)₁₂]³⁶⁻