Three-Dimensional Chirality Transfer in Rubrene Multilayer Islands on Au(111)

Pivetta, Marina; Blüm, Marie-Christine; Patthey, F.; Schneider, W. D.

doi:10.1021/jp8104024

Cited by 32 publications

(28 citation statements)

References 33 publications

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“…The fact that each domain was rotated a small angle from the substrate’s high symmetry axis rendered them chiral 4. 5c, 7a, 9b, 26 Each tri‐lobe structure consisted exclusively of either clockwise‐ or counterclockwise‐rotated domains, but never a mixture of the two, indicating that the self‐assembly was enantiospecific. As each tri‐lobe unit is homochiral, we use “+” and “−” chirality labels, indicating either a +14° or −14° rotation from the high‐symmetry directions of the Cu(111) substrate (determined within <1° error, see Experimental Section), in order to signify the chirality of each distinct tri‐lobe unit as shown in the subsequent figures.…”

Section: Resultsmentioning

confidence: 99%

Spontaneous Transmission of Chirality through Multiple Length Scales

Iski

Tierney

Jewell

et al. 2011

Chemistry A European J

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The hierarchical transfer of chirality in nature, from the nano-, to meso-, to macroscopic length scales, is very complex, and as of yet, not well understood. The advent of scanning probes has allowed chirality to be monitored at the single molecule or monolayer level and has opened up the possibility to track enantiospecific interactions and chiral self-assembly with molecular-scale detail. This paper describes the self-assembly of a simple, model molecule (naphtho[2,3-a]pyrene) that is achiral in the gas phase, but becomes chiral when adsorbed on a surface. This polyaromatic hydrocarbon forms a stable and reversibly ordered system on Cu(111) in which the transmission of chirality from single surface-bound molecules to complex 2D chiral architectures can be monitored as a function of molecular packing density and surface temperature. In addition to the point chirality of the surface-bound molecule, the unit cell of the molecular domains was also found to be chiral due to the incommensurate alignment of the molecular rows with respect to the underlying metal lattice. These molecular domains always aggregated in groups of three, all of the same chirality, but with different rotational orientations, forming homochiral "tri-lobe" ensembles. At a larger length scale, these tri-lobe ensembles associated with nearest-neighbor tri-lobe units of opposite chirality at lower packing densities before forming an extended array of homochiral tri-lobe ensembles at higher converges. This system displayed chirality at a variety of size scales from the molecular (≈1 nm) and domain (≈5 nm) to the tri-lobe ensemble (≈10 nm) and extended array (>25 nm) levels. The chirality of the tri-lobe ensembles dictated how the overall surface packing occurred and both homo- and heterochiral arrays could be reproducibly and reversibly formed and interchanged as a function of surface coverage. Finally, these chirally templated surfaces displayed remarkable enantiospecificity for naphtho[2,3-a]pyrene molecules adsorbed in the second layer. Given its simplicity, reversibility, and rich degree of order, this system represents an ideal test bed for the investigation of symmetry breaking and the hierarchical transmission of chirality through multiple length scales.

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Section: Resultsmentioning

confidence: 99%

Spontaneous Transmission of Chirality through Multiple Length Scales

Iski

Tierney

Jewell

et al. 2011

Chemistry A European J

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“…[17] Some aspects of the self-assembly in two [18,19] and three [20] dimensions, of twodimensional tiling, [21] and of the electronic properties [22,23] of rubrene on Au(111) have already been reported. Here the focus lies on the coverage-dependent assembly of rubrene on gold (111) and (100) as well as silver (111) and (100) surfaces with the aim to elucidate the influence of the electronic and geometric structure of the surface on the self-assembly process.…”

Section: Introductionmentioning

confidence: 99%

Coverage‐Dependent Self‐Assembly of Rubrene Molecules on Noble Metal Surfaces Observed by Scanning Tunneling Microscopy

et al. 2010

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Coverage-dependent self-assembly of rubrene molecules on different noble metal surfaces, Au(111) and Au(100), Ag(111) and Ag(100), is presented. On Au(111), the homochiral supramolecular assemblies evolve with increasing rubrene coverage from very small structures composed of a few molecules, to honeycomb islets, and to one-dimensional chains of supramolecular pentamers. At higher coverage, the racemic mixture of molecules forms close-packed islands. On Au(100), chains of pentamers and two different types of densely packed islands are formed. On the Ag surfaces, exclusively close-packed islands are created, independently of the rubrene coverage. Moreover, the role of the chiral nature of the molecules in the self-assembly process is discussed, as well as the existence of different molecular conformers depending on the supramolecular assembled phase. The observed differences and similarities reflect the influence of the electronic properties and the geometric structure of the various substrates on molecular self-assembly.

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“…Thus, P enantiomers are in the second layer of the λ domains (λ 2nd ), and M enantiomers are in the second layer of the ρ domains (ρ 2nd ). This structure is in contrast to the multilayer structure of chiral rubrene, for which racemic mirror domains were reported for the top layer 29…”

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confidence: 99%

Disappearing Enantiomorphs: Single Handedness in Racemate Crystals

Parschau

Ernst

2015

Angew Chem Int Ed

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Although crystallization is the most important method for the separation of enantiomers of chiral molecules in the chemical industry, the chiral recognition involved in this process is poorly understood at the molecular level. We report on the initial steps in the formation of layered racemate crystals from a racemic mixture, as observed by STM at submolecular resolution. Grown on a copper single-crystal surface, the chiral hydrocarbon heptahelicene formed chiral racemic lattice structures within the first layer. In the second layer, enantiomerically pure domains were observed, underneath which the first layer contained exclusively the other enantiomer. Hence, the system changed from a 2D racemate into a 3D racemate with enantiomerically pure layers after exceeding monolayer-saturation coverage. A chiral bias in form of a small enantiomeric excess suppressed the crystallization of one double-layer enantiomorph so that the pure minor enantiomer crystallized only in the second layer.

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Three-Dimensional Chirality Transfer in Rubrene Multilayer Islands on Au(111)

Cited by 32 publications

References 33 publications

Spontaneous Transmission of Chirality through Multiple Length Scales

Spontaneous Transmission of Chirality through Multiple Length Scales

Coverage‐Dependent Self‐Assembly of Rubrene Molecules on Noble Metal Surfaces Observed by Scanning Tunneling Microscopy

Disappearing Enantiomorphs: Single Handedness in Racemate Crystals

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