Metalloxane Cage Compounds as an Element-Block

  • Takahiro GunjiEmail author
  • Satoru Tsukada


A titanium phosphonate cluster with a formula of [Ti43-O)(OiPr)5(μ-OiPr)3(PhPO3)3]·thf was synthesized by the reaction of titanium tetraisopropoxide with phenylphosphonic acid in tetrahydrofuran and the following hydrolysis. The titanium cluster phosphonate was mixed with poly(dimethylsiloxane) (PDMS), poly(methylsilsesquioxane), poly(ethoxysilsesquioxane), poly(methyl methacrylate) (PMMA), poly(vinyl alcohol) (PVA), poly(4-vinylphenol), poly(styrene-co-allyl alcohol), or poly(bisphenol A-co-epichlorohydrin) to form a hybrid film. The mechanical strengths and strains of PDMS hybrids were very low. The tensile strengths and elongations of PMMA hybrids increased with the increase in the titanium cluster concentration. The tensile strengths and elongations of PVA hybrids were highest when the titanium cluster concentration was 10 wt%.


Element-block Titanium phosphonate cluster Organic-inorganic hybrid Poly(methyl methacrylate) Poly(vinyl alcohol) 



This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “New Polymeric Materials Based on Element-Blocks (No.2401)” (JSPS KAKENHI Grant Number JP24102008). This work was supported by JSPS KAKENHI Grant Number JP16K17951.

Shinji Ogihara, Ryuta Kitamura, and Ryosuke Matsuzaki are greatly acknowledged for their technical assistance in the tensile strength measurement.


  1. 1.
    Chujo Y, Tanaka K (2015) New polymer materials based on element–blocks. Bull Chem Soc Jpn 88:633–643CrossRefGoogle Scholar
  2. 2.
    Kanezashi M, Shioda T, Gunji T, Tsuru T (2012) Gas permeation properties of silica membranes with uniform pore sizes derived from polyhedral oligomeric silsesquioxane. AICHE J 58:1733–1743CrossRefGoogle Scholar
  3. 3.
    Tanaka K, Yamane H, Mitamura K, Watase S, Matsukawa K, Chujo Y (2014) Transformation of sulfur to organic–inorganic hybrids employed by networks and their application for the modulation of refractive indices. J Polym Sci Part A Polym Chem 52:2588–2595CrossRefGoogle Scholar
  4. 4.
    Cordes DB, Lickiss PD, Rataboul F (2010) Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chem Rev 110:2081–2173CrossRefGoogle Scholar
  5. 5.
    Bradley DC, Mehrotra RC, Rothwell IP, Singh A (2001) Alkoxo and aryloxo derivatives of metals. Academic, San DiegoGoogle Scholar
  6. 6.
    Schubert U (2004) Organofunctional metal oxide clusters as building blocks for inorganic-organic hybrid materials. J Sol-Gel Sci Techn 31:19–24CrossRefGoogle Scholar
  7. 7.
    Rozes L, Steunou N, Fornasieri G, Sanchez C (2006) Titanium-oxo clusters, versatile nanobuilding blocks for the design of advanced hybrid materials. Monatsh Chem 137:501–528CrossRefGoogle Scholar
  8. 8.
    Gross S (2011) Oxocluster-reinforced organic–inorganic hybrid materials: effect of transition metal oxoclusters on structural and functional properties. J Mater Chem 21:15853–15861CrossRefGoogle Scholar
  9. 9.
    Schubert U (2011) Cluster-based inorganic–organic hybrid materials. Chem Soc Rev 40:575–582CrossRefGoogle Scholar
  10. 10.
    Kickelbick G (2006) Hybrid materials. Wiley VCH, WeinheimCrossRefGoogle Scholar
  11. 11.
    Guerrero G, Mutin PH, Vioux A (2000) Mixed nonhydrolytic/hydrolytic sol−gel routes to novel metal oxide/phosphonate hybrids. Chem Mater 12:1268–1272CrossRefGoogle Scholar
  12. 12.
    Guerrero G, Mehring M, Mutin PH, Dahan F, Vioux A (1999) Syntheses and single-crystal structures of novel soluble phosphonate- and phosphinato-bridged titanium oxo alkoxides. J Chem Soc Dalton Trans:1537–1538Google Scholar
  13. 13.
    Mehring M, Guerrero G, Dahan F, Mutin PH, Vioux A (2000) Syntheses, characterizations, and single-crystal x-ray structures of soluble titanium alkoxide phosphonates. Inorg Chem 39:3325–3332CrossRefGoogle Scholar
  14. 14.
    Czakler M, Artner C, Schubert U (2013) Influence of the phosphonate ligand on the structure of phosphonate-substituted titanium oxo clusters. Eur J Inorg Chem:5790–5796CrossRefGoogle Scholar
  15. 15.
    Czakler M, Artner C, Schubert U (2014) Acetic acid mediated synthesis of phosphonate-substituted titanium Oxo clusters. Eur J Inorg Chem 2014:2038–2045CrossRefGoogle Scholar
  16. 16.
    Czakler M, Artner C, Schubert U (2015) Titanium oxo/alkoxo clusters with both phosphonate and methacrylate ligands. Monatsh Chem 146:1249–1256CrossRefGoogle Scholar
  17. 17.
    Kalita L, Kalita AC, Murugavel R (2014) Organotitanium phosphates with free P–OH groups: synthesis, spectroscopy and solid state structures. J Organomet Chem 751:555–562CrossRefGoogle Scholar
  18. 18.
    Sheldrick GM (1996) SADABS, program for Siemens area detector absorption correction. University of Göttingen, GermanyGoogle Scholar
  19. 19.
    Sheldrick GM (1997) SHELXS-97, program for crystal structure solution. University of Göttingen, GermanyGoogle Scholar
  20. 20.
    Armarego WLF, Chai C (2012) Purification of laboratory chemicals, 7th edn. Elsevier, OxfordGoogle Scholar
  21. 21.
    Otsuka T, Chujo Y (2010) Poly(methyl methacrylate) (PMMA)-based hybrid materials with reactive zirconium oxide nanocrystals. Polym J 42:58–65CrossRefGoogle Scholar
  22. 22.
    Julián B, Gervais C, Cordoncillo E, Escribano P, Babonneau F, Sanchez C (2003) Synthesis and characterization of transparent PDMS-metal-oxo based organic–inorganic nanocomposites. Chem Mater 15:3026–3034CrossRefGoogle Scholar
  23. 23.
    Hayami R, Wada K, Sagawa T, Tsukada S, Watase S, Gunji T (2017) Preparation and properties of organic-inorganic hybrid polymer films using [Ti4(μ 3-O)(OiPr)5(μ-OiPr)3(O3PPh)3]·thf. Polym J 49:223–228CrossRefGoogle Scholar
  24. 24.
    Guńko VM, Borysenko MV, Pissis P, Spanoudaki A, Shinyashiki N, Sulim IY, Kulik TV, Palyanytsya BB (2007) Polydimethylsiloxane at the interfaces of fumed silica and zirconia/fumed silica. Appl Surf Sci 253:7143–7156CrossRefGoogle Scholar
  25. 25.
    Adachi K, Hirano T (2008) Good linear relationship between logarithms of Eigen’s water exchange constants for several divalent metal ions and activation energies of corresponding metal-catalyzed alkoxysilane hydrolysis in ethylene-propylene copolymer system. Eur Polym J 44:542–549CrossRefGoogle Scholar
  26. 26.
    Svetich GW, Voge AA (1972) The crystal and molecular structure of sym-trans-di-μ-phenoxyhexaphenoxydiphenolatodititanium (IV). Acta Crystallogr B 28:1760CrossRefGoogle Scholar
  27. 27.
    Glaser RH, Wilkes GL (1988) Structure property behavior of polydimethylsiloxane and poly(tetramethylene oxide) modified TEOS based sol-gel materials V. effect of titaniumisopropoxide incorporation. Polym Bull 19:51–57CrossRefGoogle Scholar
  28. 28.
    Liu M, Sun J, Sun Y, Bock C, Chen Q (2009) Thickness-dependent mechanical properties of polydimethylsiloxane membranes. J Micromech Microeng 19:35028–35031. CrossRefGoogle Scholar
  29. 29.
    Lee DC, Jang LW (1996) Preparation and characterization of PMMA–clay hybrid composite by emulsion polymerization. J Appl Polym Sci 61:1117–1122CrossRefGoogle Scholar

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© Springer Nature Singapore Pte Ltd. 2019

Authors and Affiliations

  1. 1.Department of Pure and Applied Chemistry, Faculty of Science and TechnologyTokyo University of ScienceNodaJapan
  2. 2.Advanced Automotive Research Collaborative Laboratory, Graduate School of EngineeringHiroshima UniversityHigashi-Hiroshima CityJapan

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