Organic-inorganic hybrid zeolite materials containing an organic framework have been synthesized by partially superseding a lattice oxygen atom by a methylene group. The use of methylene-bridged organosilane as a silicon source gives zeolite materials containing an organic group as lattice (ZOL), with several zeolitic phases such as the MFI and the LTA structures. Through various characterization methods, the presence of methylene frameworks (Si-CH2-Si) that replace siloxane bonds (Si-O-Si) has been verified, although the Si-C bonds are partly cleaved to give rise to terminal methyl groups. The shape-selective lipophilicity of a ZOL material indicates that it is not a physical mixture of conventional zeolite and amorphous organic-containing material but contains a genuine organic-inorganic hybrid zeolite.

A novel type of organic−inorganic hybrid zeolite has been successfully synthesized, in which lattice oxygen atoms are partially superseded by methylene groups. Various types of hybrid materials with the LTA, MFI, and *BEA structures are obtained from an organosilane in which a methylene group bridges two silicon atoms under synthesis conditions similar to those for conventional zeolites. The presence of a methylene group in the framework is demonstrated by 29Si and 13C MAS NMR and IR, although the Si−C bonds are partially cleaved during the hydrothermal synthesis to give rise to terminal methyl groups. The organic framework is thermally stable enough to remain after the combustion of the occluded organic structure directing agents (SDAs). The thermal stability of the organic framework is much higher than that in amorphous materials synthesized from the same silicon source and is dependent on the zeolite structures. The SDA-free materials not only show microporosity like ordinary zeolites but also exhibit distinctively high lipophilicity/hydrophobicity in a shape-selective way. These findings clearly indicate that these materials are not physical mixtures of conventional inorganic zeolites and amorphous organic-containing materials but contain true organic−inorganic hybrid zeolites.

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