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Ionic Hydrogen Bonds Controlling Two‐Dimensional Supramolecular Systems at a Metal Surface
Author(s) -
Payer Dietmar,
Comisso Alessio,
Dmitriev Alexandre,
Strunskus Thomas,
Lin Nian,
Wöll Christof,
DeVita Alessandro,
Barth Johannes V.,
Kern Klaus
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601325
Subject(s) - trimesic acid , hydrogen bond , supramolecular chemistry , ionic bonding , carboxylate , crystallography , scanning tunneling microscope , chemistry , x ray photoelectron spectroscopy , molecule , xanes , intermolecular force , deprotonation , spectroscopy , materials science , stereochemistry , ion , nanotechnology , crystal structure , organic chemistry , physics , nuclear magnetic resonance , quantum mechanics
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.