Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Crystalline layered sodium RUB-18 of the general formula Na(2)Si(8)O(17)center dot nH(2)O was organofunctionalized after prior cetyltrimethylammonium ion intercalation. The intermediate cetyltrimethylammonium-exchanged RUB-18 (CTA-RUB-18) was used with three different types of silane coupling reagents: 3-aminopropyltriethoxysilane (N), N-3-trimethoxysilylpropylethylenediamine (2 N) and N-3-trimethoxysilylpropyldiethylenetriamine (3 N). All silylated derivatives were successfully synthesized through a methodology based on the use of small amounts of the silylating agents, with the conventional reflux procedure. The organofunctionalized materials were characterized by X-ray diffraction, chemical analysis of carbon, hydrogen and nitrogen, infrared spectroscopy, thermogravimetry and scanning electron microscopy. The organosilyl pendant chains were covalently inserted onto the intercalated layered RUB-18 compound as shown by the structural evidence illustrated by (29)Si and (13)C NMR spectroscopy in the solid state. Correlations between the interlammelar distance (d) and the number of grafted organosilyl chains (n) on the silicate surface as a function of the number of atoms (n(a)) in the pendant chains were obtained, represented by the equations: d = 0.65 + 0.32n(a) and n = 3.71-0.29n(a), respectively. These synthesized inorganic-organic nanostructured hybrids may be applied for the construction of new nanomaterials, starting from hydrated layered silicates. (C) 2009 Elsevier Inc. All rights reserved.12841699158164Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)