Ionic hydrogen bonds controlling two-dimensional supramolecular systems at a metal surface |
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| Authors: | Payer Dietmar Comisso Alessio Dmitriev Alexandre Strunskus Thomas Lin Nian Wöll Christof Devita Alessandro Barth Johannes V Kern Klaus |
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| Institution: | 1. Max Planck Institut für Festk?rperforschung, Heisenbergstra?e 1, 70563 Stuttgart, Germany, Fax: (+49)?711‐689‐1662;2. INFM‐DEMOCRITOS National Simulation Center and Center of Excellence for Nanostructured Materials (CENMAT), University of Trieste, Italy;3. Lehrstuhl für Physikalische Chemie 1, Ruhr Universit?t Bochum, Universit?tsstra?e 150, 44780 Bochum, Germany;4. Physics Department, King's College London, Strand, London WC2R?2LS, UK;5. Departments of Chemistry and Physics & Astronomy, University of British Columbia, Vancouver, B.C. V6T?1Z4, Canada;6. Institut de Physique des Nanostructures, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland |
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| Abstract: | Hydrogen-bond formation between ionic adsorbates on an Ag(111) surface under ultrahigh vacuum was studied by scanning tunneling microscopy/spectroscopy (STM/STS), X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and molecular dynamics calculations. The adsorbate, 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA), self-assembles at low temperatures (250-300 K) into the known open honeycomb motif through neutral hydrogen bonds formed between carboxyl groups, whereas annealing at 420 K leads to a densely packed quartet structure consisting of flat-lying molecules with one deprotonated carboxyl group per molecule. The resulting charged carboxylate groups form intermolecular ionic hydrogen bonds with enhanced strength compared to the neutral hydrogen bonds; this represents an alternative supramolecular bonding motif in 2D supramolecular organization. |
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| Keywords: | ab initio calculations carboxylic acids hydrogen bonds scanning tunneling microscopy supramolecular self‐assembly |
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