Supramolecular Architectures on Surfaces Formed through Hydrogen Bonding Optimized in Three Dimensions

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  • Miao Yu, Denmark
  • Nataliya Kalashnyk, Denmark
  • Wei Xu, Denmark
  • Régis Barattin, France
  • Youness Benjalal, Morocco
  • Erik Lægsgaard, Denmark
  • Ivan Stensgaard, Denmark
  • Mohamed Hliwa, Morocco
  • Xavier Bouju, France
  • André Gourdon, France
  • Christian Joachim, France
  • Flemming Besenbacher
  • Trolle René Linderoth
  • Interdisciplinary Nanoscience Center
  • Department of Physics and Astronomy
  • iNano-School
Supramolecular self-assembly on surfaces, guided by hydrogen bonding interactions, has been widely studied, most often involving planar compounds confined directly onto surfaces in a planar two-dimensional (2-D) geometry and equipped with structurally rigid chemical functionalities to direct the self-assembly. In contrast, so-called molecular Landers are a class of compounds that exhibit a pronounced three-dimensional (3-D) structure once adsorbed on surfaces, arising from a molecular backboard equipped with bulky groups which act as spacer legs. Here we demonstrate the first examples of extended, hydrogen-bonded surface architectures formed from molecular Landers. Using high-resolution scanning tunnelling microscopy (STM) under well controlled ultrahigh vacuum conditions we characterize both one-dimensional (1-D) chains as well as five distinct long-range ordered 2-D supramolecular networks formed on a Au(111) surface from a specially designed Lander molecule equipped with dual diamino-triazine (DAT) functional moieties, enabling complementary NH...N hydrogen bonding. Most interestingly, comparison of experimental results to STM image calculations and molecular mechanics structural modeling demonstrates that the observed molecular Lander-DAT structures can be rationalized through characteristic intermolecular hydrogen bonding coupling motifs which would not have been possible in purely planar 2-D surface assembly because they involve pronounced 3-D optimization of the bonding configurations. The described 1-D and 2-D patterns of Lander-DAT molecules may potentially be used as extended molecular molds for the nucleation and growth of complex metallic nanostructures.
Original languageEnglish
JournalACS Nano
Volume4
Issue7
Pages (from-to)4097-109
Number of pages13
ISSN1936-0851
DOIs
Publication statusPublished - 27 Jul 2010

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