Molecular mapping of poly(methyl methacrylate) super-helix stereocomplexes† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc02971b

In this study, by using X-ray powder diffraction profiles as blueprints, we successfully mapped the most probable molecular-level structural arrangement of the PMMA super-helix stereocomplexes through molecular dynamic simulations. Molecular-level resolution of the PMMA triple-helix supramolecule was not previously achievable by experimental methods. After constructing molecular models of stereoregular complexes composed of linear itand st-PMMAs, our all-atom molecular dynamics simulations identified the stereocomplex structure that best reproduces experimental diffraction profiles and thermodynamic properties as a double helix of isotactic (it-)PMMA with a helical pitch of 1.8 nm and 9 units per turn surrounded by a single helix of syndiotactic (st-)PMMA with an average helical pitch of 0.9 nm and 20 units per turn. The it-/stcomplexing stoichiometry in the PMMA triple-helix is therefore 9 : 20. This presents the first all-atom model of the it-/st-PMMA triple-helix stereocomplex that accurately fits experimental X-ray diffraction profiles. In addition, the simulation results revealed the outer st-PMMA helix of the PMMA stereocomplex has a fiber diameter of at least 1.85 nm and adopts a non-ideal helical geometry. Furthermore, through dynamic simulations, surprising new sights into the effect of the structural configuration of the PMMA stereocomplex (i.e., helical pitch and direction, and tilt angle) on the physical properties of their crystal structures were obtained. Those crystal properties include X-ray diffraction profile, packing density, chain–chain spacing, chain width and cohesive energy density.