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Si(OCH 2 Fc) 4 : Synthesis, Electrochemical Behavior, and Twin Polymerization
Author(s) -
Schliebe Christian,
Pfaff Ulrike,
Gemming Thomas,
Lochenie Charles,
Weber Birgit,
Lang Heinrich
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500464
Subject(s) - chemistry , polymerization , cyclic voltammetry , monomer , thermogravimetry , polymer , differential scanning calorimetry , hybrid material , polymer chemistry , differential pulse voltammetry , electrochemistry , inorganic chemistry , chemical engineering , organic chemistry , electrode , physics , engineering , thermodynamics
The preparation and twin polymerization of the twin monomer Si(OCH 2 Fc) 4 [Fc = Fe(η 5 ‐C 5 H 4 )(η 5 ‐C 5 H 5 )] ( 2 ) by the reaction of FcCH 2 OH ( 1 ) with SiCl 4 in the presence of pyridine was explored. The electronic properties of 2 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 of 2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG–MS). Upon heating 2 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 of 2 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 of 2 and SBS to silicon dioxide spheres ( d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained.