Hybrid iron(ii) phthalocyaninatoclathrochelates with a terminal reactive vinyl group and their organo-inorganic polymeric derivatives: synthetic approaches, X-ray structures and copolymerization with styrene. Issue 14 (24th March 2022)

• Record Type: Journal Article
• Authors: Dudkin, Semyon V.; Chuprin, Alexander S.; Belova, Svetlana A.; Vologzhanina, Anna V.; Zubavichus, Yan V.; Kaletina, Polina M.; Shundrina, Inna K.; Bagryanskaya, Elena G.; Voloshin, Yan Z.
• Is Part Of: Dalton transactions. Volume 51:Issue 14(2022)
• Page Start: 5645
• Page End: 5659
• Publication Date: 2022-03-24
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt04187h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Hybrid iron(ii ) (semi)clathrochelates with non-equivalent apical fragments and functionalized with one terminal reactive vinyl group were prepared and were found to be successfully copolymerized with styrene. Abstract : Hybrid metallo(iv )phthalocyaninate-capped tris-dioximate iron(ii ) complexes (termed as "phthalocyaninatoclathrochelates") with non-equivalent apical fragments and functionalized with one terminal reactive vinyl group were prepared for the first time using three different synthetic approaches: (i) transmetallation (capping group exchange) of the appropriate labile boron, antimony-capped cage precursors, (ii) capping of the initially isolated reactive semiclathrochelate intermediate, and (iii) direct one-pot template condensation of their ligand synthons on the iron(ii ) ion as a matrix. The obtained polytopic cage complexes were characterized using elemental analysis, 1 H NMR, MALDI-TOF MS and UV–vis spectra, and the single-crystal X-ray diffraction experiments. One of the obtained vinyl-terminated iron(ii ) phthalocyaninatoclathrochelates and its semiclathrochelate precursor were tested as monomers in a copolymerization reaction with styrene as the main component. These vinyl-terminated (semi)clathrochelate iron(ii ) complexes were found to be successfully copolymerized with this industrially important monomer, affording the intensely colored copolymer products. Because of a low solubility of the tested zirconium(iv ) phthalocyaninate-capped tris-nioximate monomer in styrene as a solvent, a molar ratio of 1 : 500 was used. The obtained copolymer products and the kinetics of their formation were studied using GPC, FTIR, UV–vis, TGA and DSC methods. Even at such a low concentration of the Fe, Zr-binuclear metallocomplex component, an increase in the rate of the UV-light degradation of the organo-inorganic products, as well as in their thermal stability, was observed.