Supramolecular organization of a H-bonded perylene bisimide organogelator determined by transmission electron microscopy, grazing incidence X-ray diffraction and polarized infra-red spectroscopy - Laboratoire Charles Coulomb (L2C) Accéder directement au contenu
Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2017

Supramolecular organization of a H-bonded perylene bisimide organogelator determined by transmission electron microscopy, grazing incidence X-ray diffraction and polarized infra-red spectroscopy

Résumé

An organogelator based on a N,N′-substituted H-bonding perylenebisimide (PBI-C10) self-assembles to form either a green J-type (form I) or a red H-type (form II) aggregate structure. The molecular packing of both polymorphs was determined from a combination of Transmission Electron Microscopy (TEM) (low dose electron diffraction and high resolution), Grazing incidence X-ray diffraction and polarized infrared spectroscopy. To that aim, highly oriented films have been prepared by mechanical rubbing at controlled film temperature and DFT calculations were performed to identify representative vibrational IR bands and their associated polarizations. H-Bonding between amides generates either a rectangular columnar phase (form I) in the dried gel or a hexagonal packing of supramolecular 21/1 helices with a long period of 97 Å (form II) in annealed thin films. In aligned films of form I, polarized FTIR spectroscopy helps determine the orientation of both intermolecular H-bonds and the PBI core with respect to the substrate. In form II, PBI-C10 molecules assemble into pairs to form off-centered 21/1 helices whose helical axis is made of strongly H-bonded amides. TEM investigations show that three 21/1 helices are packed in a frustrated trigonal structure formed by H-bonding. The Form I → Form II transformation implies a redistribution of a single population of strong intra-columnar H-bonds between amides in form I to a mixture of strong and weak H-bonds in the supramolecular helices, the strong H-bonds forming the spine of the helices.
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Dates et versions

hal-01759253 , version 1 (05-04-2018)

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Alexandru Sarbu, Patrick Hermet, David Maurin, David Djurado, Laure Biniek, et al.. Supramolecular organization of a H-bonded perylene bisimide organogelator determined by transmission electron microscopy, grazing incidence X-ray diffraction and polarized infra-red spectroscopy. Physical Chemistry Chemical Physics, 2017, 19 (48), pp.32514-32525. ⟨10.1039/c7cp06761e⟩. ⟨hal-01759253⟩
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