Hybrid iron() phthalocyaninatoclathrochelates with a terminal reactive vinyl group and their organo-inorganic polymeric derivatives: synthetic approaches, X-ray structures and copolymerization with styrene

• Published in: Dalton transactions : an international journal of inorganic chemistry 2022-04, Vol.51 (14), p.5645-5659
• Main 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
• Format: Article
• Language: English
• Subjects: Antimony; Cages; Capping; Chemical analysis; Condensates; Coordination compounds; Copolymerization; Copolymers; Iron; Metallography; Monomers; NMR; Nuclear magnetic resonance; Photodegradation; Precursors; Single crystals; Styrenes; Thermal stability; Ultraviolet radiation; Zirconium
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt04187h

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. 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.