Mesoscale Polarization by Geometric Frustration in Columnar Supramolecular Crystals.
Columnar supramolecular phases with polarization along the columnar axis have potential for the development of ultrahigh-density memories as every single column might function as a memory element. By investigating structure and disorder for four columnar benzene-1,3,5-trisamides by total X-ray scattering and DFT calculations, we demonstrate that the column orientation, and thus the columnar dipole moment, is receptive to geometric frustration if the columns aggregate in a hexagonal rod packing. The frustration suppresses conventional antiferroelectric order and heightens the sensitivity towards collective intercolumnar packing effects. The latter finding allows for the building up of mesoscale domains with spontaneous polarization. Our results suggest how the complex interplay between steric and electrostatic interactions is influenced by a straightforward chemical design of the molecular synthons to create spontaneous polarization and to adjust mesoscale domain size.
Inorganic Chemistry III, University of Bayreuth, Universitätsstrasse 30, 95447, Bayreuth, Germany.
Christoph S
CS
Zehe
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK.
Joshua A
JA
Hill
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK.|Current address: ISIS, Rutherford Appleton Laboratory, Chilton, Didcot, OX11 0QX, UK.
Nicholas P
NP
Funnell
Macromolecular Chemistry I, University of Bayreuth, Universitätsstrasse 30, 95447, Bayreuth, Germany.
Klaus
K
Kreger
Inorganic Chemistry III, University of Bayreuth, Universitätsstrasse 30, 95447, Bayreuth, Germany.
Kasper P
KP
van der Zwan
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK.
Andrew L
AL
Goodwin
Macromolecular Chemistry I, University of Bayreuth, Universitätsstrasse 30, 95447, Bayreuth, Germany.
Hans-Werner
0000-0002-1761-1153
HW
Schmidt
Inorganic Chemistry III, University of Bayreuth, Universitätsstrasse 30, 95447, Bayreuth, Germany.
Jürgen
0000-0002-7278-7952
J
Senker
Ising model; organic ferroelectrics; self-assembly; supramolecular chemistry; total X-ray scattering