Self-assembly of strongly dipolar molecules on metal surfaces

The Journal of Chemical Physics
Donna A KunkelAxel Enders

Abstract

The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C6H2(⋯ NHR)2(⋯ O)2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the ...Continue Reading

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Citations

Jan 12, 2016·The Journal of Physical Chemistry Letters·Donna A KunkelAxel Enders
Mar 19, 2016·Langmuir : the ACS Journal of Surfaces and Colloids·Jens NiederhausenNorbert Koch
Jul 15, 2015·Langmuir : the ACS Journal of Surfaces and Colloids·Andrew KozbialLei Li
Apr 20, 2016·Journal of the American Chemical Society·Jeffrey J SchwartzPaul S Weiss
Oct 11, 2016·Chemical Reviews·Oksana Ostroverkhova
Apr 29, 2016·Journal of Physics. Condensed Matter : an Institute of Physics Journal·S BeniwalA Enders
Jun 17, 2016·ChemistryOpen·María J MayoralDavid González-Rodríguez
Oct 28, 2019·Chemical Communications : Chem Comm·Qiang SunRoman Fasel
Sep 15, 2017·Beilstein Journal of Nanotechnology·Ryan D BrownS Alex Kandel
Sep 15, 2015·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Pierre Braunstein
Sep 10, 2016·Nanotechnology·Sang Yong SongJungpil Seo
Nov 15, 2020·The Journal of Chemical Physics·Ilya G Shenderovich
Dec 22, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Tianchao NiuMiao Zhou
Oct 28, 2019·Langmuir : the ACS Journal of Surfaces and Colloids·Oreste De LucaRaffaele Giuseppe Agostino

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