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

Stepanow, Sebastian; Lin, Nian; Payer, Dietmar; Schlickum, Uta; Klappenberger, Florian; Zoppellaro, Giorgio; Rüben, Mario; Brune, Harald; Barth, Johannes V.; Kern, Klaus

doi:10.1002/ange.200603644

Cited by 72 publications

(27 citation statements)

References 60 publications

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“…Examples include, among many supramolecular surface nanostructures involving coordination bonds, Cr-p-terphenyldinitrile on Au (111), 205 Fe-terephthalic acid on Cu(100), 206 , 207 Fe-biphenolate and Co-dicarbonitrile on Ag(111), 208 Fe-and Cu-trimesic acid on Cu(110), 209 diiron-diterephthalate on Cu(100), 210 Co-dicyanoazobenzene on Au (111), 211 Co-dicarbonitrilepolyphenyl on Ag(111), 212 Co-4,4'-(ethyne-1,2-diyl)di-benzonitrile on Ag(111), 213 Cu-1,3,8,10-tetraazaperopyrene on Cu(111), 214,215 Cu-thiolate on Cu (111), 216 Mn-carboxylate on Au (111), 217 Au-cyanosexiphenyl on Au (111), 218 and the coordination between admolecules with alkali metals on Au (111), 219,220,221 Pb-tetracyanonaphtho-quinodimethane on Pb (111), 222 and Cs atoms with aromatic carboxylic acids on Cu(100). 171 Moreover, the formation of isolated organometallic chains on Au (111) was observed.…”

Section: Metal-organicmentioning

confidence: 99%

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

et al. 2017

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This review aims at giving the readers the basic concepts needed to understand two-dimensional bimolecular organizations at the vacuum–solid interface. The first part describes and analyzes molecules–molecules and molecules–substrates interactions. The current limitations and needs in the understanding of these forces are also detailed. Then, a critical analysis of the past and recent advances in the field is presented by discussing most of the key papers describing bicomponents self-assembly on solid surface in an ultrahigh vacuum environment. These sections are organized by considering decreasing molecule–molecule interaction strengths (i.e. starting from strong directional multiple H bonds up to weaker nondirectional bonds taking into account the increasing fundamental role played by the surface). Finally, we conclude with some research directions (predicting self-assembly, multi-components systems, and nonmetallic surfaces) and potential applications (porous networks and organic surfaces).

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Section: Metal-organicmentioning

confidence: 99%

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

et al. 2017

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“…In this respect, regular porous networks are especially promising: They act as templates for the positioning of molecules or metal atoms and clusters onto well-defined sites within the cavities 5−8 as well as on the ligand molecules. 9 Moreover, depending on the metal atoms used for the coordination nodes, regular arrays of transition-metal 10,11 or rare earth atoms 12 can be created.…”

Section: ■ Introductionmentioning

confidence: 99%

Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)

2015

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We report on low-temperature scanning tunneling microscopy and spectroscopy measurements on NC-Ph 3 -CN molecules adsorbed at 300 K on a Cu(111) surface. Upon cooling, the molecules form chain and honeycomb structures, incorporating Cu adatoms supplied by the substrate as metal linkers. In these assemblies, the molecules align along two main directions, with a relative abundance that depends on the coordination number and on the bond length. We show spectroscopic data about the unoccupied molecular orbitals and investigate the patterns obtained by depositing different amounts of molecules. Comparison of these results with the ones obtained for NC-Ph 5 -CN molecules on the same substrate enables us to establish a hierarchy of the different interaction forces at work in the system. ■ INTRODUCTIONSupramolecular chemistry at surfaces is a topic of widespread interest because low-dimensional architectures with specific functionalities can be created. 1−4 A detailed understanding of the mechanism underlying the self-assembly of the various organic and metal−organic networks is important to realize the desired morphology, chemical composition, and eventually functionality. In this respect, regular porous networks are especially promising: They act as templates for the positioning of molecules or metal atoms and clusters onto well-defined sites within the cavities 5−8 as well as on the ligand molecules. 9 Moreover, depending on the metal atoms used for the coordination nodes, regular arrays of transition-metal 10,11 or rare earth atoms 12 can be created.Molecular adsorption and assembly are controlled by several competing interactions. 13−16 For the case of metal−organic porous networks, there are the van der Waals forces between the organic molecules and the surface and the corrugation of this potential energy surface upon translation and rotation of the molecules. A second ingredient is the potential energy surface felt by the metal coordination atoms, that is, their preferred adsorption sites and their diffusion barriers. Finally, there are the bond angle, distance, and coordination number of the metal−organic coordination bond.To shed light on the hierarchy of these energies, we report here on the self-assembly of NC-Ph 3 -CN molecules on Cu(111). When deposited on the substrate kept at room temperature, upon cooling NC-Ph 3 -CN molecules form chain and honeycomb structures and the molecules align with orientations that deviate from the crystallographic high symmetry directions of the surface. The comparison with the motifs formed by NC-Ph 5 -CN molecules on the same substrate 17 enables us to estimate which interaction dominates in each case, depending on the number of phenyl rings in the system. To complement the characterization of the observed metal−organic structures, we report spectroscopic data for the molecular orbitals. Moreover, the dependence of the obtained structures on the molecular coverage is discussed.

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“…Eine (111)-Oberfläche wurde wegen ihrer hexagonalen Symmetrie gewählt, die durch Templateffekte Winkel von 1208 im Adsorbatgitter stabilisieren kann. [27] Die Gasphasenabscheidung von DMTP 1 auf Cu(111) bei einer Substrattemperatur von 300 K führt in Übereinstimmung mit der Literatur und bestätigt durch Rçntgenphotoelektronen-spektren zur Spaltung der C-Br-Bindungen (siehe die Hintergrundinformation, Abbildung S1). Die RTM-Aufnahmen in Abbildung 1 zeigen, dass die m-Terphenylen-Fragmente längliche Inseln bilden, die aus Zickzack-Ketten bestehen.…”

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