Tin Oxide Nanoparticles and SnO2/SiO2 Hybrid Materials by Twin Polymerization Using Tin(IV) Alkoxides. Issue 11 (19th September 2013)

• Record Type: Journal Article
• Authors: Leonhardt, Christian; Brumm, Susann; Seifert, Andreas; Cox, Gerhard; Lange, Arno; Rüffer, Tobias; Schaarschmidt, Dieter; Lang, Heinrich; Jöhrmann, Nathanael; Hietschold, Michael; Simon, Frank; Mehring, Michael
• Is Part Of: ChemPlusChem. Volume 78:Issue 11(2013:Nov.)
• Page Start: 1400
• Page End: 1412
• Publication Date: 2013-09-19
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201200242
• Languages: English
• ISSNs: 2192-6506

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Twin polymerization was used to prepare composite materials composed of SnO<sub>2</sub> nanoparticles entrapped in a polymer matrix. Novel, well‐defined tin‐containing molecular precursors, so‐called twin monomers, were synthesized by transesterification starting from Sn(OR)<sub>4</sub> (R=<italic>t</italic>Bu, <italic>t</italic>Am) to give Sn(OCH<sub>2</sub>C<sub>4</sub>H<sub>3</sub>O)<sub>4</sub> (<bold>1</bold>), [Sn(OCH<sub>2</sub>C<sub>4</sub>H<sub>3</sub>S)<sub>4</sub><bold>⋅</bold>HOCH<sub>2</sub>C<sub>4</sub>H<sub>3</sub>S]<sub>2</sub> (<bold>2</bold>), [Sn(OCH<sub>2</sub>‐2‐OCH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>)<sub>4</sub><bold>⋅</bold>HOCH<sub>2</sub>‐2‐OCH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>]<sub>2</sub> (<bold>3</bold>), [Sn(OCH<sub>2</sub>‐2, 4‐(OCH<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)<sub>4</sub><bold>⋅</bold>HOCH<sub>2</sub>‐2, 4‐(OCH<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>2</sub> (<bold>4</bold>), 2, 2′‐spirobi[4<italic>H</italic>‐1, 3, 2‐benzodioxastannine] (<bold>5</bold>), 2, 2′‐spirobi[6‐methylbenzo(4<italic>H</italic>‐1, 3, 2)‐dioxastannine] (<bold>6</bold>), and 2, 2′‐spirobi[6‐methoxybenzo(4<italic>H</italic>‐1, 3, 2)dioxastannine] (<bold>7</bold>). <sup>13</sup>C and <sup>119</sup>Sn NMR spectroscopy in the solid state and in solution as well as IR spectroscopy and elemental analysis were used to characterize the tin alkoxides. The molecular structures of compounds <bold>2</bold> and <bold>3</bold> were determined by single‐crystal X‐ray diffraction analysis. The moisture sensitivity of the tin(IV) alkoxides was demonstrated by the formation of the tin oxocluster [Sn<sub>3</sub>(μ<sub>3</sub>‐O)(μ<sub>2</sub>‐OH)(μ<sub>2</sub>‐OCH<sub>2</sub>C<sub>4</sub>H<sub>3</sub>S)<sub>3</sub>(OCH<sub>2</sub>C<sub>4</sub>H<sub>3</sub>S)<sub>6</sub>(HOCH<sub>2</sub>C<sub>4</sub>H<sub>3</sub>S)]<sub>2</sub> (<bold>2 a</bold>), a hydrolysis product of compound <bold>2</bold>. Polymerization reactions in the melt (for <bold>1</bold> and <bold>5</bold>) and in solution (for <bold>2</bold>–<bold>4</bold>) resulted in cross‐linked nanocomposites of the type polymer/SnO<sub>2</sub>. Subsequent oxidation of the composites gave SnO<sub>2</sub> with BET surface areas up to 178 m<sup>2</sup> g<sup>−1</sup>. Simultaneous twin polymerization of compounds <bold>5</bold>–<bold>7</bold> with the silicon derivative 2, 2′‐spirobi[4<italic>H</italic>‐1, 3, 2‐benzodioxasiline] resulted in the formation of polymer/SnO<sub>2</sub>/SiO<sub>2</sub> hybrid materials. Oxidation gave porous materials with SnO<sub>2</sub> nanoparticles embedded in a silica network with BET surface areas up to 378 m<sup>2</sup> g<sup>−1</sup>. The silica acts as a crystal growth inhibitor, which prevents sintering of the SnO<sub>2</sub> nanoparticles 20–32 nm in size.</p> </abstract>