Metal−Organic Honeycomb Nanomeshes with Tunable Cavity Size

Schlickum, Uta; Decker, Régis; Klappenberger, Florian; Zoppellaro, Giorgio; Klyatskaya, Svetlana; Rüben, Mario; Silanes, Iñaki; Arnau, A.; Kern, Klaus; Brune, Harald; Barth, Johannes V.

doi:10.1021/nl072466m

Cited by 311 publications

(361 citation statements)

References 29 publications

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“…31 This leads to mesoscopically well-ordered honeycomb nanomeshes, providing open pores, the size of which is tuned by the length of the employed molecular bricks. 32 …”

Section: Resultsmentioning

confidence: 99%

Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

et al. 2008

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Self-assembly techniques allow for the fabrication of highly organized architectures with atomiclevel precision. Here, we report on molecular-level scanning tunneling microscopy observations demonstrating the supramolecular engineering of complex, regular, and long-range ordered periodic networks on a surface atomic lattice using simple linear molecular bricks. The length variation of the employed de novo synthesized linear dicarbonitrile polyphenyl molecules translates to distinct changes of the bonding motifs that lead to hierarchic order phenomena and unexpected changes of the surface tessellations. The achieved 2D organic networks range from a close-packed chevron pattern via a rhombic network to a hitherto unobserved supramolecular chiral kagomé lattice.

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“…31 This leads to mesoscopically well-ordered honeycomb nanomeshes, providing open pores, the size of which is tuned by the length of the employed molecular bricks. 32 …”

Section: Resultsmentioning

confidence: 99%

Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

et al. 2008

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“…11,30 In that case, Co adatoms were codeposited with the molecules to provide coordination centers. A honeycomb network is obtained for both ligands.…”

Section: ■ Discussionmentioning

confidence: 99%

“…NC-Ph 3 -CN molecules 11 were evaporated from a molecular effusion cell at 145°C on the substrate kept at room temperature (RT). The sample was then cooled to the scanning tunneling microscope (STM) measurement temperature of 5 K. 18 The tunneling parameters are given in the Figure captions, and the modulation amplitudes for the spectroscopy measurements are peak-to-peak values.…”

Section: ■ Experimental Methodsmentioning

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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“…The first parameter, multiplicity, has recently been shown to play a central role in the formation of convergent and divergent two‐dimensional (2D) coordination networks on metal surfaces 2, 3, 4, 5, 6, 7, 8, 9, 10, 11. In the low‐multiplicity, convergent case, ditopic ligands of high symmetry form monolayer coordination networks with co‐sublimed metal atoms, such as cobalt, on low‐index metal surfaces 9. The growth of highly regular and periodic arrangements is due to the preference for a single binding motif, which is enhanced by self‐correction mechanisms.…”

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Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers

et al. 2016

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The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism‐driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [FeII 4 L 4]8+ complexes were determined by X‐ray diffraction, and the distinctness of the products was confirmed by ion‐mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (FeII spin crossover vs. a blocked FeII high‐spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology.

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Metal−Organic Honeycomb Nanomeshes with Tunable Cavity Size

Cited by 311 publications

References 29 publications

Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

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

Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers

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Metal−Organic Honeycomb Nanomeshes with Tunable Cavity Size

Cited by 311 publications

References 29 publications

Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

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

Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers

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