Supramolecular nanolayer reconfiguration after molecular intercalation

We examined the structural reconfiguration after intercalating foreign additives, that is, tetramethoxysilane (TMOS), within already formed supramolecular nanolayers of hexadecyltrimethoxysilane (HDTMS). Our experiments indicated that the newly formed interdigitated structure is a thermodynamically more stable configuration. Even after the HDTMS formed initial bilayer-by-bilayer structures, mixing of these aggregates with foreign additives at room temperature can change the original structure to a more compact configuration (i.e., interdigitated). Our MD simulations further revealed that the most favorable organization for this interdigitated stacking appears to be a formation of relatively small domains of HDTMS and TMOS molecules, supporting our proposal of a heterogeneous mixing before reorganization. Although the coassembly of binary or multiple building blocks has previously been used to modify a supramolecule or to produce a supramolecular composite, the modification of already formed supramolecules via molecular intercalation, examined here, provides a flexible path for decorating more advanced supramolecules without disturbing their complex assembly conditions. © 2011 American Chemical Society.