Metallionen‐Gitterarchitekturen: funktionelle supramolekulare Metallkomplexe

Abstract

Jüngste Entwicklungen auf dem Gebiet der supramolekularen Koordinationschemie haben Übergangsmetallkomplexe mit Gitterstruktur ins Blickfeld der Forschung gerückt. Die Synthesen dieser komplexen molekularen Einheiten beruhen auf Selbstorganisationsprozessen, in denen die Zielverbindungen durch Koordination organischer Liganden an Metallionen in einer Stufe aus einer Vielzahl von Komponenten thermodynamisch gesteuert aufgebaut werden. Die organischen Liganden und die Metallionen bestimmen die photophysikalischen, elektrochemischen und magnetischen Eigenschaften der Gitterkomplexe, zusätzlich können jedoch auch “kollektive” Eigenschaften auftreten. Funktionelle Gitterkomplexe sind interessant für die Nanotechnologie, z. B. hinsichtlich der Entwicklung einer (supra)molekularen Informationsspeicherung und ‐verarbeitung. Das Aufbringen dieser Komplexe auf Oberflächen führt zu ausgedehnten matrixartigen Anordnungen von Metallionen mit bisher unerreichten Dichten adressierbarer Elemente.

Surface‐Assisted Assembly of 2D Metal–Organic Networks That Exhibit Unusual Threefold Coordination Symmetry

“…[2][3][4][5][6][7][8] This strategy was recently applied to low dimensions by assembling regular molecular architectures from organic molecules and transition-metal centers directly on solid surfaces. [9, 10] A variety of surface-supported molecular network structures has been made accessible by the general application of a surface-assisted metal-coordination method to metal centers and aromatic polycarboxylic acids on metal surfaces.…”

Templated Growth of Metal–Organic Coordination Chains at Surfaces

“…[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).…”

“…[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).…”

Molecular Tectonics on Surfaces: Bottom‐Up Fabrication of 1D Coordination Networks That Form 1D and 2D Arrays on Graphite

“…[5] In particular, the self-assembly of metal-ligandbased architectures at surfaces is a promising and versatile method for the fabrication of 2D metal-ion arrays. [6, 7] Indeed, the correct choice of the ligand-metal pair made it possible to fabricate various thermodynamically stable nanoscale patterns of bipyridine-based complexes adsorbed on surfaces. [8] Scanning tunneling microscopy (STM) and spectroscopy can provide direct and quantitative insight into the nanoscale properties of supramolecular architectures by addressing and manipulating assemblies with a submolecular resolution.…”

“…[6, 7] Indeed, the correct choice of the ligand-metal pair made it possible to fabricate various thermodynamically stable nanoscale patterns of bipyridine-based complexes adsorbed on surfaces. [8] Scanning tunneling microscopy (STM) and spectroscopy can provide direct and quantitative insight into the nanoscale properties of supramolecular architectures by addressing and manipulating assemblies with a submolecular resolution.[9] Up to now, STM characterizations of metal-ligand self-assembly of terpyridine-based architectures have been focused on the study of single-molecule complexes that form self-organized monolayers, [10] gridlike assemblies, [6,11] or hexameric macrocycles. [12] As stated above, although considerable effort has been devoted to the design and formation of 3D crystals composed of organic tectons and metal centers, [13] the use of a molecular tectonics approach for the generation of 2D crystalline metalloorganic patterns and arrays at surfaces has so far not been explored.…”