Building Supramolecular Nanostructures at Surfaces by Hydrogen Bonding

Barth, Johannes V.; Weckesser, Jens; Cai, Chengzhi; Günter, Peter; Bürgi, Lukas; Jeandupeux, O.; Kern, Klaus

doi:10.1002/(sici)1521-3773(20000403)39:7<1230::aid-anie1230>3.0.co;2-i

Cited by 380 publications

(341 citation statements)

References 13 publications

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“…For example, hydrogen-bond lengths generally tend to be larger within networks on metal substrates than in crystal structures of the corresponding molecules. [3,8,10,[13][14][15] The restriction to a substrate not only modifies existing chiral properties, but novel and interesting chiral effects that are not possible for bulk materials also arise. [7,14,[16][17][18] Moreover, the interaction with the metal substrate can dictate a new conformation that differs remarkably from the geometry exhibited in the crystal phase and changes the functionality, as often experienced for porphyrins [19] and adaptive peptide or amino acid species.…”

Section: Introductionsupporting

confidence: 68%

“…For simplicity and taking into account that p-conjugated organic molecules often adopt a planar adsorption geometry, [3,5,8,17] we firstly hypothesize a planar conformation and superimpose models of molecules of types A and B onto the STM image, the size of which is calibrated with the atomic resolution of the plain AgA C H T U N G T R E N N U N G (111) surface (inset). This preliminary model indicates that only one hydrogen bond of a NH···O type is present, which features a N···O (H···O) distance of 3.7 (2.7 ).…”

Section: Chain Formation On Surfacesmentioning

confidence: 99%

“…[2] For two-dimensional (2D) patterning, molecular building blocks that were already successfully employed in three-dimensional (3D) supramolecular chemistry are often used. [3][4][5][6][7] Systems based on planar molecules have been reported to build up the same bonding motifs in 2D as well as in 3D environments both for homomolecular [8][9][10] and for heteromolecular cases. [5,6,11] The resulting surface-confined architectures are influenced by the substrate on which the assembly takes place.…”

Section: Introductionmentioning

confidence: 99%

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Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

et al. 2008

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We report on a multi‐technique investigation of the supramolecular organisation of N,N‐diphenyl oxalic amide under differently dimensioned environments, namely three‐dimensional (3D) in the bulk crystal, and in two dimensions on the Ag(111) surface as well as on the reconstructed Au(111) surface. With the help of X‐ray structure analysis and scanning tunneling microscopy (STM) we find that the molecules organize in hydrogen‐bonded chains with the bonding motif qualitatively changed by the surface confinement. In two dimensions, the chains exhibit enantiomorphic order even though they consist of a racemic mixture of chiral entities. By a combination of the STM data with near‐edge X‐ray absorption fine‐structure spectroscopy, we show that the conformation of the molecule adapts such that the local registry of the functional group with the substrate is optimized while avoiding steric hindrance of the phenyl groups. In the low coverage case, the length of the chains is limited by the Au(111) reconstruction lines restricting the molecules into fcc stacked areas. A kinetic Monte Carlo simulated annealing is used to explain the selective assembly in the fcc stacked regions.

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Section: Introductionsupporting

confidence: 68%

Section: Chain Formation On Surfacesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

et al. 2008

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“…This reveals that the 1-D aggregates actually consist of PVBA twin chains, which form well-ordered nanogratings at the micrometer scale. 23 The molecular axes are oriented along the chain direction, in agreement with the expected formation of hydrogen bonds between PVBA endgroups. Although atomic resolution of the close-packed Ag surface is routinely achieved with the STM employed for this study, simultaneous resolution of substrate atomic lattice and imaging of molecules proved to be impossible.…”

Section: Diffusion-limited Aggregation At Low Temperaturesmentioning

confidence: 99%

“…20 Finally, chirality may be expressed at the supramolecular level in discrete molecular assemblies at surfaces which are stabilized by noncovalent bonds. [21][22][23][24] The understanding of chiral ordering at surfaces is in its infancy. The objective of the present investigations is to elucidate stereochemical effects in the chiral supramolecular assembly of organic molecules at surfaces.…”

Section: Introductionmentioning

confidence: 99%

Stereochemical Effects in Supramolecular Self-Assembly at Surfaces: 1-D versus 2-D Enantiomorphic Ordering for PVBA and PEBA on Ag(111)

et al. 2002

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Abstract:We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems.

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Self-Assembled Two-Dimensional Molecular Host-Guest Architectures From Trimesic Acid

et al. 2002

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The adsorption of 1,3,5-Benzenetricarboxylic (Trimesic) Acid (TMA) to a single crystal graphite surface has been studied under Ultra High Vacuum conditions. This work focuses on inducing a particular self-assembly structure by OMBE (Organic Molecular Beam Epitaxy), characterized by periodic non-dense-packing of the molecules. Two coexisting phases could be imaged with sub-molecular resolution by STM. Induced by directed hydrogen bonding, the organic molecules built in both cases a two-dimensional grid architecture with molecular caves. This two-dimensional host structure can accept single trimesic acid guest molecules in different positions.

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Building Supramolecular Nanostructures at Surfaces by Hydrogen Bonding

Cited by 380 publications

References 13 publications

Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

Stereochemical Effects in Supramolecular Self-Assembly at Surfaces: 1-D versus 2-D Enantiomorphic Ordering for PVBA and PEBA on Ag(111)

Self-Assembled Two-Dimensional Molecular Host-Guest Architectures From Trimesic Acid

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