title: Molecularly tethered amphiphiles as 3-D supramolecular assembly platforms: unlocking a trapped conformation.
abstract: A fluorous biphasic hexa(3,5-substituted-phenyl)benzene (HPB), analogous to semifluorinated alkanes, was synthesized such that precise chemical and orthogonally directed, supramolecular placement of amphiphilic side chains at their bulk density was achieved. The grafting or tethering of incommensurate hydrocarbon and fluorocarbon chains to the rotationally flexible HPB core inextricably links intermolecular phase separation with intramolecular conformational behavior and results in rich self-assembly. The self-assembled structure was studied with polarized optical microscopy, differential scanning calorimetry, X-ray scattering, and (19)F magic-angle spinning solid-state NMR and found to be kinetically trapped with mixed fluorocarbon and hydrocarbon side chains, despite packing into a lattice defined by the HPB scaffold. The addition of 1% of the parent biphasic diphenylacetylene unlocks the frustrated conformation in the HPB, resulting in the formation of a thermodynamically favorable bilayer structure.
authors.affiliation: Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany. chris.clark@liquidia.com
authors.forename: Christopher G
authors.initials: CG
authors.lastname: Clark
authors.forename: George A
authors.initials: GA
authors.lastname: Floudas
authors.forename: Young Joo
authors.initials: YJ
authors.lastname: Lee
authors.forename: Robert
authors.initials: R
authors.lastname: Graf
authors.forename: Hans W
authors.initials: HW
authors.lastname: Spiess
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D002152:Calorimetry, Differential Scanning; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D014961:X-Ray Diffraction
chemical_list: D001555:Benzene Derivatives; D006845:Hydrocarbons, Fluorinated