Porous organic-inorganic materials with tunable textural characteristics were synthesized using the top-down process by intercalating silsesquioxanes and polyhedral oligomeric siloxanes of different types between crystalline zeolite-derived layers. The influence of key parameters such as (i) linker nature (pure hydrocarbon, S-, N-containing); (ii) chain length in alkyl- and aryl bis(trialkoxysilyl) derivatives; (iii) denticity of the organic precursor molecules; (iv) nature and size of side chain in mono(trialkoxysilyl) substrates; (v) rigidity of the chain (saturated vs. unsaturated, aliphatic vs. aromatic); (vi) nature and size of leaving group on the structural and textural properties of formed hybrids was carefully addressed. It was established, that the optimal silsesquioxane appropriate for the formation of zeolite-derived hybrids with high textural characteristics should possess short alkyl or long aryl chains, relatively small leaving groups and denticity larger than 3. Addition of polydentate low-molecular binder improved the structural and textural characteristics of hybrids, especially when using bulky or hydrophilic linkers.

EaStChem School of Chemistry The University of St Andrews St Andrews KY16 9ST Scotland UK Email

J Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic v v i Dolejškova 3 CZ 182 23 Prague 8 Czech Republic Email

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