Heat-induced formation of one-dimensional coordination polymers on Au(111): an STM study

Pham, Tuan Anh; Song, Fei; Alberti, M. N.; Nguyen, Manh‐Thuong; Trapp, Nils; Thilgen, Carlo; Diederich, François; Stöhr, Meike

doi:10.1039/c5cc04940g

Cited by 33 publications

(37 citation statements)

References 33 publications

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“…There is no evidence from either XPS or the STM analysis that Au-ad-atoms from the substrate are involved in the formation of similar ladder-like assemblies. 43 Deposition of ligands 1-3 was also carried out on a Cu(111) substrate held at room temperature (see Fig. S11 for XPS multilayer result) which provides Cu-ad-atoms for coordination from the surface during preparation.…”

Section: On-surface Assembliesmentioning

confidence: 99%

The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms

et al. 2018

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A comparative investigation of crystal growth from solution and on-surface assembly in vacuo between copper and three 4'-(2-R-pyrimidin-5-yl)-4,2':6',4''-terpyridines, with R = H (1), Me (2), or Et (3), is presented. In solution, ligand 3 combines with copper(II) acetate or copper(I) triflate in MeOH solution to give [Cu(OAc)(3)] or {[Cu(3)(OMe)(MeOH)][CFSO]·MeOH}. In [Cu(OAc)(3)], paddle-wheel {Cu(μ-OAc)} nodes direct the assembly of one-dimensional (1D) zigzag chains which pack into two-dimensional (2D) sheets. In {[Cu(3)(OMe)(MeOH)][CFSO]·MeOH}, the solvent is a ligand and also generates {Cu(μ-OMe)} units which function as planar 4-connecting nodes to generate a 2D (4,4) net with ligand 3. On Au(111) or Cu(111) surfaces in vacuo, no additional solvent or anions are involved in the assembly. The different substituents in 1, 2, or 3 allow precise molecular resolution imaging in scanning tunneling microscopy. On Au(111), 1 and 2 assemble into close-packed assemblies, while 3 forms a regular porous network. The deposition of Cu adatoms results in reorganization leading to ladder-shaped surface metal-organic motifs. These on-surface coordination assemblies are independent of the 4'-substituent in the 4,2':6',4''-tpy and are reproduced on Cu(111) where Cu adatoms are available during the deposition and relaxation process at room temperature. Upon annealing at elevated temperatures, the original surface assemblies of 1 and 3 are modified and a transition from ladders into rhomboid structures is observed; for 2, a further quasi-hexagonal nanoporous network is observed.

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Section: On-surface Assembliesmentioning

confidence: 99%

The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms

et al. 2018

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“…By embracing the supramolecular approach, 1-3 that relies on spontaneous association of suitably designed small molecules into one-, two-and three-dimensional superstructures, this spatial control may be attained via self-assembly of suitably designed molecular building blocks. 25 STM was used to explore the self-assembly of porphyrins under ultra-high vacuum (UHV) on graphite 26 and metallic substrates [27][28][29] , and under ambient conditions on graphite supports. [4][5][6][7][8][9][10][11][12][13][14][15][16] Self-assembly at interfaces enables the controlled positioning of functional units with sub-nanometer precision over areas of micrometers and thereby allows the fine-tuning of numerous properties of the resulting nanostructures [17][18][19][20][21] for technological applications, in particular in optics, catalysis, electronics and sensing.…”

Section: Introductionmentioning

confidence: 99%

Molecular design driving tetraporphyrin self-assembly on graphite: a joint STM, electrochemical and computational study

et al. 2016

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Tuning the intermolecular interactions among suitably designed molecules forming highly ordered self-assembled monolayers is a viable approach to control their organization at the supramolecular level. Such a tuning is particularly important when applied to sophisticated molecules combining functional units which possess specific electronic properties, such as electron/energy transfer, in order to develop multifunctional systems. Here we have synthesized two tetraferrocene-porphyrin derivatives that by design can selectively self-assemble at the graphite/liquid interface into either face-on or edge-on monolayer-thick architectures. The former supramolecular arrangement consists of two-dimensional planar networks based on hydrogen bonding among adjacent molecules whereas the latter relies on columnar assembly generated through intermolecular van der Waals interactions. Scanning Tunneling Microscopy (STM) at the solid-liquid interface has been corroborated by cyclic voltammetry measurements and assessed by theoretical calculations to gain multiscale insight into the arrangement of the molecule with respect to the basal plane of the surface. The STM analysis allowed the visualization of these assemblies with a sub-nanometer resolution, and cyclic voltammetry measurements provided direct evidence of the interactions of porphyrin and ferrocene with the graphite surface and offered also insight into the dynamics within the face-on and edge-on assemblies. The experimental findings were supported by theoretical calculations to shed light on the electronic and other physical properties of both assemblies. The capability to engineer the functional nanopatterns through self-assembly of porphyrins containing ferrocene units is a key step toward the bottom-up construction of multifunctional molecular nanostructures and nanodevices.

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“…[14,15] Here,weused this technique to follow the solvation of ah ydrogen-bonded solid in real space.T he hydrogenbond-assisted formation of supramolecular networks on surfaces has been thoroughly investigated by scanning probe microscopic techniques in recent years. [16][17][18][19][20][21] These networks may be understood as low-dimensional crystals,which makes them excellent test subjects for the investigation of solvation processes by STM. To maximize accessibility for water, we synthesized amolecule that is able to form hydrogen-bonded one-dimensional chains.For this purpose,3-methoxy-9-diazofluorene (MDAF) was chosen, which consists of af luorene backbone that is functionalized with two polar groups,namely am ethoxy group of intermediate polarity and ah ighly polar diazo group.W ec hose Ag(111) as as ubstrate because of its low reactivity towards adsorbates at low temperatures according to d-band theory.…”

mentioning

confidence: 99%

Imaging the Solvation of a One‐Dimensional Solid on the Molecular Scale

et al. 2018

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We have observed the inversion of the solvation environment of ao ne-dimensional solid by low-temperature scanning tunneling microscopy. Adsorption of 3-methoxy-9diazofluorene on Ag(111) yields highly oriented supramolecular chains,w hich are then exposed to water molecules.T he annealing of dry and water-decorated chains results in diametrically opposed outcomes.While the former simply leads to an increase in chain length and number,t he latter results in acomplete loss of order and produces water clusters decorated with the organic molecule.

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Heat-induced formation of one-dimensional coordination polymers on Au(111): an STM study

Cited by 33 publications

References 33 publications

The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms

The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms

Molecular design driving tetraporphyrin self-assembly on graphite: a joint STM, electrochemical and computational study

Imaging the Solvation of a One‐Dimensional Solid on the Molecular Scale

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