title: Solid-state organization of semifluorinated alkanes probed by 19F MAS NMR spectroscopy.
abstract: Bulk-phase self-assembly of a series of semifluorinated alkanes (SFAs) with hydrocarbon chains of varying length has been investigated by 19F NMR spectroscopy. At room temperature, a single 19F resonance for the terminal sCF3 group was observed at -81.7 ppm for perfluorododecylhexane (F12H6), whereas a sCF3 resonance was seen at -82.5 ppm for perfluorododecyldodecane (F12H12) and perfluorododecyleicosane (F12H20). This difference in chemical shift position is ascribed to the different molecular packing geometries, i.e., a monolayer lamellar structure for F12H6 vs a bilayer lamellar organization for F12H12 and F12H20. Moreover, in F12H12, a solid-solid phase transition from bilayer to monolayer lamellae can be followed by 19F NMR spectroscopy. 1H/19F-->13C CPMAS experiments indicated that the phase transition is accompanied by disordering of hydrocarbon chains, but does not involve a significant conformational change in the fluorocarbon chains. Yet, a change in the 19F T1 relaxation times was found to occur at the phase transition temperature, suggesting a change in the packing environments of the fluorocarbon chains. Two-dimensional exchange NMR experiments yielded cross-peaks between terminal sCF3 and inner sCF2CH2s moieties for the high-temperature monolayer phase, providing clear evidence for the spatial proximity between these groups. On the basis of these findings, we propose a model for the phase transition involving bilayer lamellae and monolayer lamellae with hydrocarbon and fluorocarbon interdigitation.
authors.affiliation: Max Planck Institute for Polymer Research, Mainz, Germany.
authors.forename: Young Joo
authors.initials: YJ
authors.lastname: Lee
authors.forename: Christopher G
authors.initials: CG
authors.lastname: Clark
authors.forename: Robert
authors.initials: R
authors.lastname: Graf
authors.forename: Manfred
authors.initials: M
authors.lastname: Wagner
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
authors.forename: Hans Wolfgang
authors.initials: HW
authors.lastname: Spiess
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007554:Isotopes; D009682:Magnetic Resonance Spectroscopy; D013696:Temperature; D013997:Time Factors
chemical_list: D000473:Alkanes; D006845:Hydrocarbons, Fluorinated; D007554:Isotopes