Si(OCH2Fc)4: Synthesis, Electrochemical Behavior, and Twin Polymerization. Issue 23 (14th July 2015)

• Record Type: Journal Article
• Authors: Schliebe, Christian; Pfaff, Ulrike; Gemming, Thomas; Lochenie, Charles; Weber, Birgit; Lang, Heinrich
• Is Part Of: European journal of inorganic chemistry. Issue 23(2015)
• Page Start: 3850
• Page End: 3860
• Publication Date: 2015-07-14
• Subjects: Hybrid materials -- Nanoparticles -- Iron -- Superparamagnetism -- Electrochemistry -- Twin polymerization; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500464
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The preparation and twin polymerization of the twin monomer Si(OCH2 Fc)4 [Fc = Fe(η 5 ‐C5 H4 )(η 5 ‐C5 H5 )] (2 ) by the reaction of FcCH2 OH (1 ) with SiCl4 in the presence of pyridine was explored. The electronic properties of2 were investigated by cyclic voltammetry, square‐wave voltammetry, and UV/Vis/near‐IR spectroelectrochemistry, which showed a redox separation caused by electrostatic repulsion. Thermally induced condensation of2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG–MS). Upon heating2 to 210 °C, twin polymerization occurred and a hybrid material was formed that showed similarities with known systems derived from 2, 2′‐spirobi[4 H ‐1, 3, 2‐benzodioxasiline] (SBS), such as the nanopatterning of the formed silicon dioxide, which is characteristic for twin polymerization. Electron microscopy of this material revealed the absence of typical microstructuring found for other twin polymers, and hence, the herein presented system can be characterized as a borderline system if compared to known twin monomers such as SBS. The copolymerization of2 and SBS afforded a hybrid material from which porous carbon or silica materials containing iron oxide nanoparticles could be obtained. The oxidation state of the incorporated particles was examined by Mössbauer experiments, which confirmed that only Fe III was incorporated within the porous carbon and silica materials, respectively. The preparation of iron oxide containing porous carbon capsules was achieved by applying a mixture of2 and SBS to silicon dioxide spheres ( d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained. Abstract : The straightforward preparation of iron‐rich porous carbon and silica materials by twin polymerization of Si(OCH2 Fc)4 [Fc = Fe(η 5 ‐C5 H4 )(η 5 ‐C5 H5 )] and 2, 2′‐spirobi[4 H ‐1, 3, 2‐benzodioxasiline] is reported; the electrochemical properties of Si(OCH2 Fc)4 are discussed.