Two-dimensional metal-organic coordination networks of Mn-7,7,8,8-tetracyanoquinodimethane assembled on Cu(100): Structural, electronic, and magnetic properties

Tseng, Tzu-Chun; Chen, Lin; Shi, Xingqiang; Tait, Steven L.; Liu, Xiong; Starke, Ulrich; Lin, Nian; Zhang, Ruiqin; Minot, Christian; Hove, M. A. Van; Cerdá, Jorge I.; Kern, Klaus

doi:10.1103/physrevb.80.155458

Cited by 42 publications

(54 citation statements)

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“…To rationalize the fact that in the chains the favored orientation results in a shorter bond length compared with the one mostly found in the honeycomb, we observe that there is a clear trend linking a decreasing coordination number at the nodes and a shorter bond length. Reported values include 2.4 Å for NC-Ph 3 -CN 5-fold coordinated to Ce adatoms on Ag(111), 12 2.15 Å for TCNQ 4-fold coordinated to Mn atoms on Cu(100), 33 1.9 Å for NC-Ph n -CN 3-fold coordinated to Co atoms on Ag(111), 34 and the same value for NC-Ph 5 -CN 3-fold coordinated to Cu atoms on Cu(111). 7 A model for the irregular honeycomb pattern together with a high-resolution STM image measured with a D 2 -terminated tip 35,36 is shown in Figure 3d, with those molecules aligned along direction 1 represented in bold.…”

Section: ■ Results and Discussionmentioning

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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Section: ■ Results and Discussionmentioning

confidence: 99%

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

2015

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“…As a result, for a given combination of substrate and adsorbate, different polymorphic phases can be obtained depending on the netuning of the experimental conditions. [4][5][6][7] Hitherto, a considerable number of studies has focused either on the use of direct inter-molecular interactions, [8][9][10][11][12][13][14][15] or of coordinating metallic centers, 16 either supplied in a second deposition step, [17][18][19][20] or being already present on the surface in the form of diffusing adatoms, [21][22][23][24] to mediate the self-assembly process. On the other hand, while it is generally acknowledged that the presence of periodic molecular arrays may perturb the substrate electronic structure, [25][26][27] the role of direct moleculesurface bonding has been rarely investigated.…”

Section: Introductionmentioning

confidence: 99%

Understanding the self-assembly of TCNQ on Cu(111): a combined study based on scanning tunnelling microscopy experiments and density functional theory simulations

et al. 2016

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“…Surface‐based two‐dimensional (2D) metal–organic nanostructures (MOS) are planar and highly ordered networks formed by the coordination of metal centres to tailored functional groups of organic ligands. The incorporated metal atoms confer electronic, magnetic and catalytic properties to the network, thereby motivating extensive studies on this class of MOS driven by their potential applications in surface porous material engineering, catalysis, and information storage . The coordination bonding involves charge transfer between the metals and the organic ligands.…”

Section: Introductionmentioning

confidence: 99%

Two‐Dimensional Ketone‐Driven Metal–Organic Coordination on Cu(111)

Pia

Riello

Lawrence

et al. 2016

Chemistry A European J

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Two‐dimensional metal–organic nanostructures based on the binding of ketone groups and metal atoms were fabricated by depositing pyrene‐4,5,9,10‐tetraone (PTO) molecules on a Cu(111) surface. The strongly electronegative ketone moieties bind to either copper adatoms from the substrate or codeposited iron atoms. In the former case, scanning tunnelling microscopy images reveal the development of an extended metal–organic supramolecular structure. Each copper adatom coordinates to two ketone ligands of two neighbouring PTO molecules, forming chains that are linked together into large islands through secondary van der Waals interactions. Deposition of iron atoms leads to a transformation of this assembly resulting from the substitution of the metal centres. Density functional theory calculations reveal that the driving force for the metal substitution is primarily determined by the strength of the ketone–metal bond, which is higher for Fe than for Cu. This second class of nanostructures displays a structural dependence on the rate of iron deposition.

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Two-dimensional metal-organic coordination networks of Mn-7,7,8,8-tetracyanoquinodimethane assembled on Cu(100): Structural, electronic, and magnetic properties

Cited by 42 publications

References 35 publications

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

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

Understanding the self-assembly of TCNQ on Cu(111): a combined study based on scanning tunnelling microscopy experiments and density functional theory simulations

Two‐Dimensional Ketone‐Driven Metal–Organic Coordination on Cu(111)

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Two-dimensional metal-organic coordination networks of Mn-7,7,8,8-tetracyanoquinodimethane assembled on Cu(100): Structural, electronic, and magnetic properties

Cited by 42 publications

References 35 publications

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

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

Understanding the self-assembly of TCNQ on Cu(111): a combined study based on scanning tunnelling microscopy experiments and density functional theory simulations

Two‐Dimensional Ketone‐Driven Metal–Organic Coordination on Cu(111)

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

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