| Autor: |
Dudkin SV; Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russia. voloshin@ineos.ac.ru., Chuprin AS; Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russia. voloshin@ineos.ac.ru., Belova SA; Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russia. voloshin@ineos.ac.ru., Vologzhanina AV; Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russia. voloshin@ineos.ac.ru., Zubavichus YV; Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences, 1 Nikolskii pr., 6305590 Koltsovo, Russia., Kaletina PM; Vorozhtsov Novosibirsk Institute of Organic Chemistry Siberian Branch of Russian Academy of Sciences, 9 Lavrentiev pr., 630090 Novosibirsk, Russia., Shundrina IK; Vorozhtsov Novosibirsk Institute of Organic Chemistry Siberian Branch of Russian Academy of Sciences, 9 Lavrentiev pr., 630090 Novosibirsk, Russia., Bagryanskaya EG; Vorozhtsov Novosibirsk Institute of Organic Chemistry Siberian Branch of Russian Academy of Sciences, 9 Lavrentiev pr., 630090 Novosibirsk, Russia., Voloshin YZ; Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russia. voloshin@ineos.ac.ru.; Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, 31 Leninsky pr., 119991 Moscow, Russia. |
| Abstrakt: |
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. |
