Marked Increase in the Binding Strength between the Substrate and the Covalently Attached Monolayers of Zeolite Microcrystals by Lateral Molecular Cross-Linking between the Neighboring Microcrystals

Monolayers of cubic zeolite microcrystals (1.7 x 1.7 x 1.7 and 0.3 x 0.3 x 0.3 mum3) were assembled on glass plates through imine- or urethane-linkages between the zeolite-tethered 3-aminopropyl (AP) groups and the glass-bound benzaldehyde or isocyanate groups, which were prepared by treating AP-tethering glass plates with a large excess of terephthaldicarboxaldehyde (TPDA) or 1,4-diisocyanatobutane (DICB), respectively, in toluene. The additional treatment of the monolayers of zeolite microcrystals with TPDA or DICB led to lateral molecular cross-linking between the neighboring, closely packed zeolite microcrystals in the monolayers through AP-TPDA-AP imine or AP-DICB-AP urethane linkages between the zeolite-tethered AP groups and the newly introduced TPDA or DICB, respectively. The comparison of the binding strengths between the glass substrates and the monolayers revealed that the molecular cross-linking leads to as much as 7- and 38-fold (by average) increase in the binding strength in the cases of 1.7 x 1.7 x 1.7 and 0.3 x 0.3 x 0.3 mum3 crystals, respectively. We predict that the effect of lateral cross-linking on the binding strength will further increase with further decreasing the size of the building blocks to nanoparticles and to molecules.