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

Abstract

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.

Dysprosium-carboxylate nanomeshes with tunable cavity size and assembly motif through ionic interactions

“…A comparison to literature data reveals that the binding energy of the Dy 3d5/2 peak is in excellent agreement with Dy in a +3 oxidation state (1296 eV). 33 These results are similar to those recently reported for CsBPyDA 32 and Na-TPA 18 supramolecular architectures on Cu(100) surfaces and for Gd-carboxylate reticular networks, 29 in which a predominant ionic character of the metal-organic bond is proposed. This strongly differs from the metal-organic bond in Fe-carboxylate architectures, 31,34 where a prevalent covalent nature has been suggested.…”

“…This strongly differs from the metal-organic bond in Fe-carboxylate architectures, 31,34 where a prevalent covalent nature has been suggested. 32 Next, in order to modulate the inter-lanthanide distance of the reticular phase, we have studied the coordination of PDA and TPA modules with Dy atoms in independent experiments. The sublimation of the synthesized PDA species (cf.…”

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

“…171 Moreover, the formation of isolated organometallic chains on Au (111) was observed. The deposition of iodine-functionalized units (2',5'-diiodo-3,3",5,5"-tetramethyl-1,1':4',1"-terphenyl) on the metallic surface induces the release of iodine and allows bond formation between the molecule and diffusing gold adatoms.…”

“…For instance, Stepanow et al used cesium adatoms with four polyaryl dicarboxylic acids, which produces various chiral arrangements of the network structures. 171 However, a naive electronegativity argument does not generally apply for all metallic adsorbates because the anisotropy experienced by surface atoms induces a modification in the relative scale of electronegativity factors.…”

Stereoselectivity and electrostatics in charge-transfer Mn- and Cs-TCNQ4 networks on Ag(100)

“…The use of alkali metals in the same context has been much less explored 25,26 , although their low ionization energy may induce charging processes and lead to a potentially interesting interplay between local linkage and long-range electrostatic effects. The latter are very important because, for example, the formation of surface electric dipoles would allow some control of the interface level alignment, one of the main issues in organic electronics 27 .…”