Self-assembly of metal–organic coordination structures on surfaces

Dong, Lu; Gao, Ziang; Lin, Nian

doi:10.1016/j.progsurf.2016.08.001

Cited by 249 publications

(267 citation statements)

References 233 publications

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“…To unveil the stabilizing intermolecular bonds in these hexamers, acquiring complementary information on the chemical state of HATP is indispensable. In this respect, it is important to address the question of a possible deprotonation of the amino groups and formation of metal‐coordination bonds after room‐temperature deposition onto Cu(111) . Therefore, XP spectra were acquired from N 1s and C 1s core levels, whereby the spectra of three‐ to four‐layer‐thick films shown in Figures a, b served as references for chemically unaltered HATP molecules.…”

Section: Resultsmentioning

confidence: 52%

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

Lischka

Dong

Wang

et al. 2019

Chemistry A European J

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The interplay between the self‐assembly and surface chemistry of 2,3,6,7,10,11‐hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high‐resolution scanning tunneling microscopy (STM) and X‐ray photoelectron spectroscopy (XPS) under ultra‐high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel‐covered Cu(111). Directly after room‐temperature deposition of HATP onto pristine Cu(111), self‐assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π–d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal–organic trimer, in which three HATP molecules were coordinated by Cu3 clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)–Ni bonded networks already at room temperature. Even though fused hexagonal metal‐coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal–organic bonds.

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Section: Resultsmentioning

confidence: 52%

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

Lischka

Dong

Wang

et al. 2019

Chemistry A European J

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“…One way to circumvent this issue is by fixing molecular catalysts on a conducting solid support. Interestingly, transition metal porphyrins and similar molecular complexes are known to self‐assemble on coinage metal supports . Several studies have been devoted towards understanding the molecule‐support interaction of transition metal–porphyrins or pthalocyanines on supports such as gold, silver, copper, platinum or even non‐metal surfaces such as graphene,, graphene oxide,, and carbon nanotubes ,,.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

Siahrostami

Nørskov

2018

ChemCatChem

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It has been a long‐standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. We use density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)‐porphycenes (MPc). All the 3d metal‐porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. This work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.

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“…10 In particular, by confining the selfassembly process on solid substrates, two-dimensional (2D) structures can be formed 11,12 by exploiting a number of different intermolecular forces: from metal coordination 13,14 to hydrogen bonding 14,15 , to weaker dispersion interactions. 16 While the nature of the interactions between the molecular units is typically the key factor in determining the resulting assembly, other more subtle influences have also been reported to affect the final supramolecular structures: the chemistry and symmetry of the substrate (even for inert surfaces such as highly ordered pyrolytic graphite (HOPG) and Au(111) 17 ), the temperature, [18][19][20] the ultra-high vacuum (UHV) or solution environment, 19,21,22 the nature of the solvent, 19,[23][24][25][26][27][28] the concentration of the solute (the self-assembling molecule), 18,[29][30][31][32][33][34][35] and any co-adsorption of solvent or guest molecules 24,25,34,36,37 .…”

Section: Introductionmentioning

confidence: 99%

Molecular self-assembly of substituted terephthalic acids at the liquid/solid interface: investigating the effect of solvent

et al. 2017

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Self-assembly of three related molecules – terephthalic acid and its hydroxylated analogues – at liquid/solid interfaces (graphite/heptanoic acid and graphite/1-phenyloctane) has been studied using a combination of scanning tunnelling microscopy and molecular mechanics and molecular dynamics calculations. Brickwork-like patterns typical for terephthalic acid self-assembly have been observed for all three molecules. However, several differences became apparent: (i) formation or lack of adsorbed monolayers (self-assembled monolayers formed in all systems, with one notable exception of terephthalic acid at the graphite/1-phenyloctane interface where no adsorption was observed), (ii) the size of adsorbate islands (large islands at the interface with heptanoic acid and smaller ones at the interface with 1-phenyloctane), and (iii) polymorphism of the hydroxylated terephthalic acids’ monolayers, dependent on the molecular structure and/or solvent. To rationalise this behaviour, molecular mechanics and molecular dynamics calculations have been performed, to analyse the three key aspects of the energetics of self-assembly: intermolecular, substrate–adsorbate and solvent–solute interactions. These energetic characteristics of self-assembly were brought together in a Born–Haber cycle, to obtain the overall energy effects of formation of self-assembled monolayers at these liquid/solid interfaces.

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Self-assembly of metal–organic coordination structures on surfaces

Cited by 249 publications

References 233 publications

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

Molecular self-assembly of substituted terephthalic acids at the liquid/solid interface: investigating the effect of solvent

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