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

Abstract

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.

Substrate effect on supramolecular self-assembly: from semiconductors to metals

“…Similarly to what happens in solution chemistry, the formation of metal-organic coordination bonds on surfaces requires the deprotonation of the carboxylic acid groups. While this occurs readily on certain substrates such as Cu(100), 15,23 Cu(110) 21 or Pd(111), …”

“…Furthermore, two-dimensional (2D) MOFs could be formed by co-adsorption of d-transition metal atoms such as Fe, Co and Cu. [16][17][18][19][20][21][22][23] Due to its double-ended functionality, when TPA is absorbed in an upright geometry, it can be used for the organic passivation of inorganic surfaces such as Cu(110) 24 and TiO 2 . 25 A perpendicular binding geometry has also been reported for the adsorption of a similar molecule, 2-(trifluoromethyl)-terephthalic acid (C 6 H 3 CF 3 (COOH) 2 ), from solution onto fluorine-terminated Si(111).…”

Formation of Bioinorganic Complexes by the Corrosive Adsorption of (S)-Proline on Ni/Au(111)

“…At all annealing temperatures, a single asymmetric peak is present which was fitted with four components that were found to be present in the O 1s spectrum of proline on Au(111) 30 . The resulting spectra are comprised of four components analogous to the behavior of proline on Au(111) 30 and trimesic acid on Cu(111), 53 however, two of these features make up >90% of the total O 1s spectrum at each annealing temperature, whilst the two smaller components are barely visible but can be seen in the expanded spectra contained in the Supporting Information ( Figure S3). A large central feature at 531.5 eV BE contributes 70-90 % of the total oxygen signal at all stages of the experiment and can be assigned to the oxygen atoms of the electronically delocalized carboxylate species.…”

Visualization of nucleation and growth of supramolecular networks on Cu(001) and Au(111)

“…Benzoic-acids adsorbed on single crystalline metal surfaces belong to the more frequently studied systems [10,11,12,13,14,15,16,17,18,19,20]. Here, the benzene rings of the molecules act as backbones, allowing a flat adsorption geometry on the metal substrates.…”

“…Most of these studies are motivated by the potential for the networks to act as flexible templates for the fabrication of novel nanoscale structures [10,11,12,20,81]. Detailed STM studies of the molecular networks and their building blocks have been performed [10,11,13,14,15,16,17,18,19]. So far, only a few studies have concentrated on thermodynamic and kinetic aspects of the growth of supramolecular domains on a mesoscopic length scale [27,54], despite the importance of both to make these networks applicable.…”