Two‐Dimensional Adatom Gas Bestowing Dynamic Heterogeneity on Surfaces

Lin, Nian; Payer, Dietmar; Dmitriev, Alexandre; Strunskus, Thomas; Wöll, Christof; Barth, Johannes V.; Kern, Klaus

doi:10.1002/ange.200461390

Cited by 49 publications

(60 citation statements)

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confidence: 98%

“…[23] These adatoms have been found by XPS analysis for similar systems to catalyze the deprotonation of the molecular carboxylic groups, [24,25] and are furthermore necessary for the formation of Cu carboxylate complexes. [23,24,26] Depositing at lower temperatures, 210 K and 250 K, resulted in disordered structures with a tip to tip bonding motif. This signature which is never observed above 300 K is characteristic for intramolecular dimeric hydrogen bonds of carboxylic groups, [20][21][22]24] thus indicating that the carboxylic groups are protonated for temperatures below 300 K. Annealing to 300 K of these structures yields to the same 1D chains described above.…”

mentioning

confidence: 98%

“…[23,24,26] Depositing at lower temperatures, 210 K and 250 K, resulted in disordered structures with a tip to tip bonding motif. This signature which is never observed above 300 K is characteristic for intramolecular dimeric hydrogen bonds of carboxylic groups, [20][21][22]24] thus indicating that the carboxylic groups are protonated for temperatures below 300 K. Annealing to 300 K of these structures yields to the same 1D chains described above. The 300 K chains typically show irregular kinks and poor long-range order.…”

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confidence: 99%

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Templated Growth of Metal–Organic Coordination Chains at Surfaces

et al. 2005

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Metal-organic coordination networks (MOCNs) formed by coordination bonding between metallic centers and organic ligands can be efficiently engineered to exhibit specific magnetic, electronic, or catalytic properties. [1][2][3][4][5][6] Instead of depositing prefabricated MOCNs onto surfaces, it has been recently shown that two dimensional (2D) MOCNs can be directly grown at metal surfaces in ultra high vacuum (UHV), thus creating highly regular 2D networks of metal atoms. [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). In order to evidence its strong 1D templating effect on organic molecules, a ligand with a triangular symmetry was selected: 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA, Figure 1c). In fact, the 3-fold rotation symmetry supports the formation of hexagonal 2D and 3D architectures, [20][21][22] therefore strongly disfavoring the linear geometry. On the isotropic Cu(100) surface, TMA forms 0D carboxylate complexes and 2D networks. [9,10] The UHV deposition of TMA on Cu(110) at 300 K results in the formation of 1D chains along the 110 direction, as observed by STM. This deposition temperature is high enough to * * The authors wish to acknowledge Nian Lin, Magalí Lingenfelder, Alexander Schneider and Giacinto Scoles for fruitful discussions, HPC-EUROPA (project #506079) and INFM Progetto Calcolo Parallelo for computer resources.

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Templated Growth of Metal–Organic Coordination Chains at Surfaces

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“…If the carboxylate group retains a negative charge upon deprotonation, hydrogen bonds of this group with neutral or positive groups of neighboring molecules will have a ionic character and thus will be considerably stronger (up to one-third of the strength of covalent bonds). On reactive substrates, deprotonation may take place at lower temperatures, especially in the presence of adatoms, [14] which lower the energetic barrier of the process. In this case, the interaction between the carboxylate ends and the metallic adatoms can lead to the formation of metal-organic networks on the surface.…”

Section: H-bond At Its Simplest: Purposedly Designed Molecules With Cmentioning

confidence: 99%

“…[14][15][16][17][18][19] The occurrence of deprotonation depends on a variety of factors, most importantly temperature and substrate reactivity. Limiting ourselves to inert surfaces and low temperatures, intermolecular interactions will be expected to involve carboxylic functionalities only.…”

Section: H-bond At Its Simplest: Purposedly Designed Molecules With Cmentioning

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Atomic‐Level Studies of Molecular Self‐Assembly on Metallic Surfaces

Tomba¹,

Ciacchi²,

Vita³

2009

Advanced Materials

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Shrinking devices to the nanoscale, while still maintaining accurate control on their structure and functionality is one of the major technological challenges of our era. The use of purposely directed self‐assembly processes provides a smart alternative to the troublesome manipulation and positioning of nanometer‐sized objects piece by piece. Here, we report on a series of recent works where the in‐depth study of appropriately chosen model systems addresses the two key‐points in self‐assembly: building blocks selection and control of bonding. We focus in particular on hydrogen bonding because of the stability, precision and yet flexibility of nanostructures based on this interaction. Complementing experimental information with advanced atomistic modeling techniques based on quantum formalisms is a key feature of most investigations. We thus highlight the role of theoretical modeling while we follow the progression in the use of more and more complex molecular building blocks, or “tectons”. In particular, we will see that the use of three‐dimensional, flexible tectons promises to be a powerful way to achieve highly sophisticated functional nanostructures. However, the increasing complexity of the assembly units used makes it generally more difficult to control the supramolecular organization and predict the assembling mechanisms. This creates a case for developing novel analysis methods and ever more advanced modeling techniques.

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

et al. 2007

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Coordination-based supramolecular chemistry, [1] with its characteristic control of the self-assembly process and intrinsic defect tolerance, has been proven to be a very efficient synthetic tool to fabricate metallosupramolecular networks of well-defined topology in one, two, and three dimensions. [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.[9] As valid for supramolecular structures in general, the structures of the two-dimensional metal-organic coordination networks (2D-MOCNs) formed are predetermined by the properties of the ligands (e.g., donor atoms and their spatial arrangement, steric crowding) and the electronic characteristics of the metal ions (e.g., involved orbitals, ionization energies). However, under 2D conditions, the realization of a given coordination algorithm might be altered by the presence of a metal substrate, which results in deviating coordination geometries for the same metal-ligand coupling in comparison to the 3D situation (e.g., in the bulk phase). Such deviation can be attributed to charge transfer or screening effects and the strict 2D confinement of ligands and metal centers imposed by the substrate, which substantially influences the characteristics of the metal-to-ligand bonding within the 2D coordination network.[10e]

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Two‐Dimensional Adatom Gas Bestowing Dynamic Heterogeneity on Surfaces

Cited by 49 publications

References 38 publications

Templated Growth of Metal–Organic Coordination Chains at Surfaces

Templated Growth of Metal–Organic Coordination Chains at Surfaces

Atomic‐Level Studies of Molecular Self‐Assembly on Metallic Surfaces

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

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