Direct Determination of POSS Cage Structure in a Self‐Assembled Ionic Bridged Silsesquioxane by Using the Total Pair Distribution Function G(r) and Density Functional Theory

Abstract

In the present study, both short‐range and long‐range structural features of an ionic bridged silsesquioxane, specifically one containing the 1,4‐diazoniabicyclo[2.2.2]octane chloride group (ISSQ), were elucidated. This ionic silsesquioxane was synthesized via direct polycondensation of a bridged organosilane precursor, without any additional functionalization step. Si‐O‐Si cage structures typical of Polyhedral Oligomeric Silsesquioxanes (POSS) were identified. The average interatomic distances of the POSS cages, including the open T8 cage and the T12 cage for the ISSQ, as well as the T8 cage for a commercially available pendant POSS were determined. It is the first report of the interatomic distance determination of POSS cage; achieved by using total pair distribution function G(r) values obtained through high‐resolution synchrotron X‐ray diffraction combined with density functional theory (DFT) calculations. The application of DFT was crucial for accurately assigning X‐ray peaks and verifying structural details. Furthermore, the analysis of X‐ray diffraction peaks and the examination of crystalline domains via transmission electron microscopy enabled the proposal of a hexagonal arrangement of Si–O–Si cages over long ranges within the ionic bridged silsesquioxane. This proposed arrangement highlights a distinctive structural organization that could impact the material's properties and applications.