Influence of Substitutional Groups on the Ordering and Crystallization of Amphiphilic Silsesquioxanes at the Air–Water Interface

We report on the surface ordering and crystallization sequences in differently organic-substituted amphiphilic polyhedral silsesquioxane (POSS) variants induced by regulated compression at the air–water interface. Such molecular systems floating at the interface serve as a model system to study dynamic crystallization mediated by weak interactions. In situ grazing incidence X-ray scattering (GIXS) measurements, performed at a synchrotron X-ray source using a liquid surface diffractometer and corroborated with Brewster angle microscopy, revealed transformations for the different POSS variants (viz. trisilanol isobutyl POSS (TBPOSS), trisilanol cyclohexyl POSS (TCHPOSS), disilanol octaisobutly POSS (DOBPOSS), and trisilanol isooctyl POSS (TOPOSS)) from a weakly correlated monolayer structure to appreciably different structural and crystalline phases in various packing schemes. GIXS measurements revealed a stable nature of the crystallization of DOBPOSS, varying degrees of metastable crystallization for TCHPOSS and TBPOSS, and complete absence of crystalline phase in TOPOSS molecules. Incidentally, for all POSS variants showing crystalline phases, the motifs always assembled in a triclinic lattice with P1̅ symmetry. For the metastable crystals, preferential surface ordering of the crystallites promotes selective crystalline planes to exhibit preferred tilt angles with respect to the interface. The structural transformations of the differently substituted POSS molecules and their variations therein are attributed to the changing balance of the hydrophobic vs hydrophilic interaction in the layers, which is determined by the anisotropic shape and distribution of substitutional groups over the nanosized core cage of the monomer, steric interaction between nearest dimeric neighbors, as well as the in-plane and out-of-plane assembly of the overlayers.