Single-Molecule Charge Transfer and Bonding at an Organic/Inorganic Interface:  Tetracyanoethylene on Noble Metals

Wegner, Daniel; Yamachika, Ryan; Wang, Yayu; Brar, Victor W.; Bartlett, Bart M.; Crommie, Michael F.

doi:10.1021/nl072217y

Cited by 88 publications

(119 citation statements)

References 28 publications

(49 reference statements)

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“…78 This electron exchange then leads to longrange, electrostatic repulsive molecule−molecule interactions as seen also for other species. 79,81 A comparison of our findings on 2H-TPP on Cu(111) with published STM data on metalated TPP or TPyP on the same substrate 48,57,62 seems further to suggest that not the ligands but rather the macrocycle metalation is controlling the self-assembly: nonmetalated molecules with different ligands (2H-TPP, TPyP) remain isolated on the Cu(111), while only metallated TPP are observed to form networks. This conclusion is backed by related studies of molecule−substrate interactions that conclude that the metal ion in the porphyrin macrocycle plays the central role in the electronic interaction between the complexes and the metal surface, which was even found to result in additional electronic states.…”

Section: Discussionsupporting

confidence: 64%

Self-Assembly and Properties of Nonmetalated Tetraphenyl-Porphyrin on Metal Substrates

et al. 2010

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IntroductionThe self-assembly of porphyrins on well-defined surfaces is attracting considerable interest because it promises to create surface patterns with nanometer dimension that exhibit specific electronic, sensoric, optic, or catalytic functionality 1-3 or even interesting magnetic properties. 4,5 The ability of porphyrin to show self-organization and to accommodate metal atoms in their macrocycle is exploited, for instance, to form metal−organic frameworks or adsorbed layers for catalysis. [6][7][8][9] The selfassembly is mainly driven by noncovalent metal−organic coordination interactions, which is well-known and important in solution-based 3D supramolecular chemistry. [10][11][12][13][14][15] Porphyrin molecules have been adsorbed onto surfaces to form supramolecular networks from solution, [16][17][18][19] electrochemically 20,21 or by thermal evaporation under vacuum conditions. [22][23][24][25][26][27][28] While there is a rich literature on the electronic structure of these adsorbates, the surface adlayer structures have also been characterized with scanning force microscopy, scanning tunneling microscopy, or X-ray absorption near-edge structure analysis. 29 The rationale of such experiments on 2D structures has been to study the long-range interactions that determine the self-assembly processes. It has been demonstrated that the bottom-up fabrication of highly organized porphyrin layers, as well as of porphyrin-based multicomponent molecular entities, depends on the interplay of molecule−molecule and substrate−molecule interactions. Molecule−substrate interactions will set limits to the mobility of the adsorbed molecules and may alter the electronic structure of the absorbed molecules, or the electronic states at the surfaces may become locally perturbed by the adsorbate. 60 A consequence is that the established concepts of solution-based coordination chemistry cannot be applied without appropriate modification. The substrate thus becomes an additional parameter to control the adsorption energy of the molecules and, hence, their diffusivity at surfaces. An intriguing demonstration of this effect is the self-assembly of porphyrins, which are decoupled from their metal substrate by insulating NaCl layers of varying thickness. 23 The interaction was shown to be dependent on the NaCl layers, and the thicker the NaCl the weaker the interaction and the more delayed the onset of network formation. The occupation of the center ring of the porphyrin may affect the molecular adsorption at surfaces. As an example, free-base or Cu-incorporated porphyrin molecules show different arrangements along step edges on Cu(100) surfaces. While 2H-TBPP bridges over the step edges, Cu-TBPP sits on either side of step edges. 27 In contrast, no difference in the network architecture was found for differently metalated TPP on Ag(111). 57 Such a subtle dependence of adsorption site on metal incorporation, if fully understood, may become useful to control the self-assembly or the properties of the molecules on surfaces.The goal...

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Section: Discussionsupporting

confidence: 64%

Self-Assembly and Properties of Nonmetalated Tetraphenyl-Porphyrin on Metal Substrates

et al. 2010

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“…13,14 In the last case, the intermolecular interactions are probably substrate mediated due to strong reshaping of the interface that has been reported for TCNE 15 and the closely related TCNQ 16 on Cu(100). Substrate mediated interactions can be expected to be rather non-directional and thus lead to close-packed molecular arrays.…”

Section: Resultsmentioning

confidence: 66%

“…[13][14][15][16] To gain insight into this problem, we have performed DFT calculations of a TCNE molecule on the Ag (111) surface. Of all the tested possibilities, the minimum energy configuration is shown in Figure 5.…”

Section: Resultsmentioning

confidence: 99%

Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks

Rodrı́guez-Fernández

Lauwaet

Herranz

et al. 2015

The Journal of Chemical Physics

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The deposition of tetracyanoethylene (TCNE) on Ag(111), both at Room Temperature (RT, 300 K) and low temperatures (150 K), leads to the formation of coordination networks involving silver adatoms, as revealed by Variable-Temperature Scanning Tunneling Microscopy. Our results indicate that TCNE molecules etch away material from the step edges and possibly also from the terraces, which facilitates the formation of the observed coordination networks. Moreover, such process is temperature dependent, which allows for different stoichiometric ratios between Ag and TCNE just by adjusting the deposition temperature. X-ray Photoelectron Spectroscopy and Density Functional Theory calculations reveal that charge-transfer from the surface to the molecule and the concomitant geometrical distortions at both sides of the organic/inorganic interface might facilitate the extraction of silver atoms from the step-edges and, thus, its incorporation into the observed TCNE coordination networks. C 2015 AIP Publishing LLC. [http://dx

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“…Namely, to achieve the long-range FM order in the system of adatoms at the TI surface one has to organize their ordered arrays [14,34,35] and prevent them from diffusion [44,47] or intercalation inside the bulk or the van der Waals gaps [34,[51][52][53][54]. Lately, a type of system which may provide these conditions were successfully grown on metallic substrates-selfassembled metal-organic coordination networks (MOCNs) [55][56][57][58][59][60][61][62][63][64]. In such experiments, strong electron acceptors like tetracyanoethylene (TCNE, C 6 H 4 ), tetracyanobenzene (TCNB, C 10 H 2 N 4 ), and tetracyanoquinodimethane (TCNQ, C 12 H 4 N 4 ) are the most frequently used molecules.…”

Section: Introductionmentioning

confidence: 99%

Breaking time-reversal symmetry at the topological insulator surface by metal-organic coordination networks

2015

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We propose a way to break the time-reversal symmetry at the surface of a three-dimensional topological insulator that combines features of both surface magnetic doping and magnetic proximity effect. Based on the possibility of organizing an ordered array of local magnetic moments by inserting them into a two-dimensional matrix of organic ligands, we study the magnetic coupling and electronic structure of such metal-organic coordination networks on a topological insulator surface from first principles. In this way, we find that both Co and Cr centers, linked by the tetracyanoethylenelike organic ligand, are coupled ferromagnetically and, depending on the distance to the topological insulator substrate, can yield a magnetic proximity effect. This latter leads to the Dirac point gap opening indicative of the time-reversal symmetry breaking.

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Single-Molecule Charge Transfer and Bonding at an Organic/Inorganic Interface: Tetracyanoethylene on Noble Metals

Cited by 88 publications

References 28 publications

Self-Assembly and Properties of Nonmetalated Tetraphenyl-Porphyrin on Metal Substrates

Self-Assembly and Properties of Nonmetalated Tetraphenyl-Porphyrin on Metal Substrates

Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks

Breaking time-reversal symmetry at the topological insulator surface by metal-organic coordination networks

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