4.6 Article

Elucidating the Structure of the Pm(3)over-barn Cubic Phase of Supramolecular Dendrimers through the Modification of their Aliphatic to Aromatic Volume Ratio

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 15, Issue 36, Pages 8994-9004

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200901324

Keywords

cubic phase; dendrimers; liquid crystals; self-assembly; X-ray diffraction

Funding

  1. National Science Foundation [DMR-0548559, DMR-0520020]
  2. American Chemical Society-Division of Organic Chemistry Graduate Research Fellowship
  3. Roche, Inc

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The synthesis, and structural and retrostructural analysis of a library of second-generation conical dendrons that self-assemble into spherical supramolecular dendrimers is reported. This library consists of amphiphilic dendrons with n-alkyl groups containing from 4 to 16 carbon atoms. The dendrons containing 6 to 16 carbon atoms in their n-alkyl groups self-assemble into spherical supramolecular dendrimers that self-organize in a Pm (3) over barn cubic lattice. The structural and retrostructural analysis of the Pm (3) over barn lattices generated from the supramolecular dendrimers demonstrated that the volume of the aromatic core of the spherical dendrimers is not dependent on the number of carbon atoms from their alkyl groups. This result facilitated the calculation of the average values of the absolute electron density of the aliphatic and aromatic domains of the spherical supramolecular dendrimers. The relative intensity of the higher order diffraction peaks of the Pm (3) over barn lattice increases as the volume of the aliphatic part of the sphere mediated by the number of carbon atoms in the n-alkyl groups decreases. This study demonstrates the maximum increase of the relative intensity of the higher order diffraction peaks of the Pm (3) over barn lattice generated from non-hollow supramolecular dendrimers.

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