Hybrid iron(II) phthalocyaninatoclathrochelates with terminal reactive vinyl group and their organo-inorganic polymeric derivatives: synthetic approaches, X-ray structures and copolymerization with styreneстатьяИсследовательская статья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 20 апреля 2022 г.
Аннотация:First hybrid metallo(IV)phthalocyaninate-capped tris-dioximate iron(II) complexes (so-called “phthalocyaninatoclatrochelates”) with non-equivalent apical fragments, functionalized with one terminal reactive vinyl group, were prepared using three different synthetic approaches: (i) by a transmetallation (capping group exchange) of the appropriate labile boron,antimony-capped cage precursors, (ii) via a capping of the initially isolated reactive semiclathrochelate intermediate, and (iii) using the direct one-pot template condensation of their ligand synthons on the iron(II) ion as a matrix. Thus obtained polytopic cage complexes were characterized using elemental analysis, 1H NMR, MALDI-TOF MS, and UV–vis spectra, and by the single crystal X-ray diffraction experiments. One of the obtained vinyl-terminated iron(II) phthalocyaninatoclathrochelates and its semiclatrochelate precursor were tested as olefin monomers in their copolymerization reaction with styrene as a main component. These vinyl-terminated (semi)clathrochelate iron(II) complexes were found to be successfully copolymerized with this industrially important monomer, thus giving the intensively colored copolymer products. Because of a low solubility of the tested zirconium(IV) phthalocyaninate-capped tris-nioximate monomer in styrene as a solvent, their molar ratio of 1:500 was used. Thus obtained copolymer products and the kinetic of their formation were studied using GPC, FTIR, UV-vis, TGA and DSC methods. Even at such a low concentration of this Fe,Zr-binuclear metallocomplex component, an increase as in the rate of UV-light degradation of these organo-inorganic products, as in their thermal stability, is found.