Deprotonation-Driven Phase Transformations in Terephthalic Acid Self-Assembly on Cu(100)

Stepanow, Sebastian; Strunskus, Thomas; Lingenfelder, Magalí; Dmitriev, Alexandre; Spillmann, Hannes; Lin, Nian; Barth, Johannes V.; Wöll, Christof; Kern, Klaus

doi:10.1021/jp046766t

Cited by 153 publications

(255 citation statements)

References 30 publications

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“…[11][12][13] As a consequence, the analysis of the oxygen energy region further confirms the simultaneous presence of intact and deprotonated carboxylic groups. Figure 4d shows the Cu2p 3/2 core level spectrum together with the results of a line shape analysis.…”

Section: Tma Deposition At Low Substrate Temperaturesmentioning

confidence: 57%

“…However, after deposition at 300 K, two contributions at higher binding energies (289.4 and 287.8 eV) are present, indicating both carboxylic and carboxylate groups, respectively ( Figure 17a). Similarly, the O1s spectra in Figure 17c show the carboxylate peak at 530.9 eV together with a broader contribution centered at 532.7, which is characteristic of hydrogenbonded carboxylic groups (with contributions from both hydroxy and carbonyl oxygens [11][12][13] ). This observation together with the XPS data for the MOCC-S phase shown in section IV A is in agreement with the RAIRS results; up to a coverage of 0.53 ML, the acid groups deprotonate and form carboxylate-copper complexes; at higher coverages, the TMA molecule adsorbs with at least one group remaining intact in the acidic form.…”

Section: High Coverage At High Temperature: the Double Chain Phasesmentioning

confidence: 83%

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Hydrogen and Coordination Bonding Supramolecular Structures of Trimesic Acid on Cu(110)

Claßen

Lingenfelder²,

Wang³

et al. 2007

J. Phys. Chem. A

120

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The adsorption of trimesic acid (TMA) on Cu(110) has been studied in the temperature range between 130 and 550 K and for coverages up to one monolayer. We combine scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), reflection absorption infrared spectroscopy (RAIRS), X-ray photoemission spectroscopy (XPS), and density functional theory (DFT) calculations to produce a detailed adsorption phase diagram for the TMA/Cu(110) system as a function of the molecular coverage and the substrate temperature. We identify a quite complex set of adsorption phases, which are determined by the interplay between the extent of deprotonation, the intermolecular bonding, and the overall energy minimization. For temperatures up to 280 K, TMA molecules are only partly deprotonated and form hydrogen-bonded structures, which locally exhibit organizational chirality. Above this threshold, the molecules deprotonate completely and form supramolecular metal-organic structures with Cu substrate adatoms. These structures exist in the form of single and double coordination chains, with the molecular coverage driving distinct phase transitions.

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Section: Tma Deposition At Low Substrate Temperaturesmentioning

confidence: 57%

Section: High Coverage At High Temperature: the Double Chain Phasesmentioning

confidence: 83%

Hydrogen and Coordination Bonding Supramolecular Structures of Trimesic Acid on Cu(110)

Claßen

Lingenfelder²,

Wang³

et al. 2007

J. Phys. Chem. A

120

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show abstract

“…17 The submonolayer of BPyDA exhibits only a single peak with a binding energy of 531.2 eV corresponding to the chemically equivalent oxygen atoms in the carboxylate moiety. 17 Thus, the molecules directly in contact with the copper surface are deprotonated under the employed experimental conditions. Upon Cs addition, the position of the peak is subjected to a small shift of 0.3 eV to a lower binding energy of 530.9 eV.…”

Section: Resultsmentioning

confidence: 99%

Rational Design of Two-Dimensional Nanoscale Networks by Electrostatic Interactions at Surfaces

et al. 2010

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The self-assembly of aromatic carboxylic acids and cesium adatoms on a Cu(100) surface at room temperature has been investigated by scanning tunneling microscopy and X-ray photoelectron spectroscopy. The highly ordered molecular nanostructures are comprised of a central ionic coupling motif between the anionic carboxylate moieties and Cs cations that generate distinctive chiral arrangements of the network structures. The primary electrostatic interaction results in highly flexible bond lengths and geometries. The adsorbate−substrate coupling is found to be important for the determination of the structures. With the use of rod-like carboxylic linker molecules, the dimension of the porous networks can be tuned through the variation of the aromatic backbone length.

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“…[23] These adatoms have been found by XPS analysis for similar systems to catalyze the deprotonation of the molecular carboxylic groups, [24,25] and are furthermore necessary for the formation of Cu carboxylate complexes. [23,24,26] Depositing at lower temperatures, 210 K and 250 K, resulted in disordered structures with a tip to tip bonding motif.…”

mentioning

confidence: 99%

Templated Growth of Metal–Organic Coordination Chains at Surfaces

et al. 2005

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Metal-organic coordination networks (MOCNs) formed by coordination bonding between metallic centers and organic ligands can be efficiently engineered to exhibit specific magnetic, electronic, or catalytic properties. [1][2][3][4][5][6] Instead of depositing prefabricated MOCNs onto surfaces, it has been recently shown that two dimensional (2D) MOCNs can be directly grown at metal surfaces in ultra high vacuum (UHV), thus creating highly regular 2D networks of metal atoms. [7][8][9][10][11][12] These grids have been pointed out to be potentially relevant for devices involving sensing, switching, and information storage. [13,14] We show here that this approach offers the additional advantage to predefine the MOCN geometry by using the substrate as template to direct the formation of novel 1D metal-organic coordination chains (MOCCs).The templating role of substrates is well known in the field of surface epitaxial growth. [15][16][17][18][19] Among the highly anisotropic substrates, the Cu(110) surface is one of the most common (Figure 1a and b). In order to evidence its strong 1D templating effect on organic molecules, a ligand with a triangular symmetry was selected: 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA, Figure 1c). In fact, the 3-fold rotation symmetry supports the formation of hexagonal 2D and 3D architectures, [20][21][22] therefore strongly disfavoring the linear geometry. On the isotropic Cu(100) surface, TMA forms 0D carboxylate complexes and 2D networks. [9,10] The UHV deposition of TMA on Cu(110) at 300 K results in the formation of 1D chains along the 110 direction, as observed by STM. This deposition temperature is high enough to * * The authors wish to acknowledge Nian Lin, Magalí Lingenfelder, Alexander Schneider and Giacinto Scoles for fruitful discussions, HPC-EUROPA (project #506079) and INFM Progetto Calcolo Parallelo for computer resources.

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Deprotonation-Driven Phase Transformations in Terephthalic Acid Self-Assembly on Cu(100)

Cited by 153 publications

References 30 publications

Hydrogen and Coordination Bonding Supramolecular Structures of Trimesic Acid on Cu(110)

Hydrogen and Coordination Bonding Supramolecular Structures of Trimesic Acid on Cu(110)

Rational Design of Two-Dimensional Nanoscale Networks by Electrostatic Interactions at Surfaces

Templated Growth of Metal–Organic Coordination Chains at Surfaces

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