A spherosilicate oligomer with eight stable silanol groups as a building block of hybrid materials

Kazufumi Kawahara, Hiroki Tachibana, Yoshiaki Hagiwara, Kazuyuki Kuroda

    Research output: Contribution to journalArticle

    12 Citations (Scopus)

    Abstract

    Diphenylsilylated double four-membered ring (D4R) spherosilicate possessing eight stable silanol groups ((R 1R 2(HO)SiO) 8Si 8O 12, R 1 and R 2 = Ph: PP(OH)-D4R) has been synthesized by silylation of D4R silicate ([Si 8O 12] 8-) with chloroethoxydiphenylsilane (ClSi(OEt)Ph 2) followed by subsequent hydrolysis. PP(OH)-D4R solid is air stable for at least 1 week. Ethoxymethylphenylsilylated and ethoxydimethylsilylated D4R oligomers (R 1R 2(EtO)SiO) 8Si 8O 12, R 1 = Me and R 2 = Ph abbreviated as MP(OEt)-D4R and R 1 and R 2 = Me as MM(OEt)-D4R) do not provide spherosilicates possessing stable silanol groups and eventually gel (MP(OEt)-D4R-G and MM(OEt)-D4R-G, respectively) as hydrolyzed solutions dry. This suggests that bulky phenyl groups effectively stabilize terminal silanols. Although the PP(OH)-D4R silanols are stable, they can be trimethylsilylated or condensed to form Si-O-Si bonds by thermal-treatment. PP(OH)-D4R on a glass substrate cross-links upon heating. The structural periodicity and distance between D4R units in the heat-treated sample are higher and longer than those of MP(OEt)-D4R-G and MM(OEt)-D4R-G due to the steric effects of the bulky Ph groups. Additionally, the silica-based gel derived from PP(OH)-D4R also possesses a higher molecularly ordered structure than that derived from a mixture of Si(OEt) 4 and Ph 2Si(OEt) 2. This means that a building block approach is efficient for preparing molecularly ordered hybrid materials. The new spherosilicate possessing silanol groups will be a useful building block for preparation of various materials such as metallosilicates and mesostructured materials.

    Original languageEnglish
    Pages (from-to)1210-1217
    Number of pages8
    JournalNew Journal of Chemistry
    Volume36
    Issue number5
    DOIs
    Publication statusPublished - 2012 May

    Fingerprint

    Hybrid materials
    Oligomers
    Gels
    Silicates
    Hydrolysis
    Heat treatment
    Silica
    Heating
    Glass
    Substrates
    Air
    Silicon Dioxide
    silanol
    Hot Temperature

    ASJC Scopus subject areas

    • Chemistry(all)
    • Catalysis
    • Materials Chemistry

    Cite this

    A spherosilicate oligomer with eight stable silanol groups as a building block of hybrid materials. / Kawahara, Kazufumi; Tachibana, Hiroki; Hagiwara, Yoshiaki; Kuroda, Kazuyuki.

    In: New Journal of Chemistry, Vol. 36, No. 5, 05.2012, p. 1210-1217.

    Research output: Contribution to journalArticle

    Kawahara, Kazufumi ; Tachibana, Hiroki ; Hagiwara, Yoshiaki ; Kuroda, Kazuyuki. / A spherosilicate oligomer with eight stable silanol groups as a building block of hybrid materials. In: New Journal of Chemistry. 2012 ; Vol. 36, No. 5. pp. 1210-1217.
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    abstract = "Diphenylsilylated double four-membered ring (D4R) spherosilicate possessing eight stable silanol groups ((R 1R 2(HO)SiO) 8Si 8O 12, R 1 and R 2 = Ph: PP(OH)-D4R) has been synthesized by silylation of D4R silicate ([Si 8O 12] 8-) with chloroethoxydiphenylsilane (ClSi(OEt)Ph 2) followed by subsequent hydrolysis. PP(OH)-D4R solid is air stable for at least 1 week. Ethoxymethylphenylsilylated and ethoxydimethylsilylated D4R oligomers (R 1R 2(EtO)SiO) 8Si 8O 12, R 1 = Me and R 2 = Ph abbreviated as MP(OEt)-D4R and R 1 and R 2 = Me as MM(OEt)-D4R) do not provide spherosilicates possessing stable silanol groups and eventually gel (MP(OEt)-D4R-G and MM(OEt)-D4R-G, respectively) as hydrolyzed solutions dry. This suggests that bulky phenyl groups effectively stabilize terminal silanols. Although the PP(OH)-D4R silanols are stable, they can be trimethylsilylated or condensed to form Si-O-Si bonds by thermal-treatment. PP(OH)-D4R on a glass substrate cross-links upon heating. The structural periodicity and distance between D4R units in the heat-treated sample are higher and longer than those of MP(OEt)-D4R-G and MM(OEt)-D4R-G due to the steric effects of the bulky Ph groups. Additionally, the silica-based gel derived from PP(OH)-D4R also possesses a higher molecularly ordered structure than that derived from a mixture of Si(OEt) 4 and Ph 2Si(OEt) 2. This means that a building block approach is efficient for preparing molecularly ordered hybrid materials. The new spherosilicate possessing silanol groups will be a useful building block for preparation of various materials such as metallosilicates and mesostructured materials.",
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