Spontaneous chiral symmetry breaking by achiral molecules in a Langmuir–Blodgett film

Viswanathan, R.; Zasadzinski, Joseph A.; Schwartz, Daniel K.

doi:10.1038/368440a0

Cited by 167 publications

(120 citation statements)

References 25 publications

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“…15a can be considered as a conglomerate of a monolayered crystal due to coexisting homochiral domains of both enantiomers. A similar observation was made early with the atomic force microscopy (AFM) [94] and many times thereafter.…”

Section: Homochiral Versus Heterochiralmentioning

confidence: 66%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

223

264

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With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self‐assembly of chiral and prochiral molecules and the principles of mirror‐symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long‐range symmetry breaking in two‐dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface‐related sources of chiral topics completes this paper.

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Section: Homochiral Versus Heterochiralmentioning

confidence: 66%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

223

264

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“…The emergence of chiral structures is documented in insoluble monolayers at the air/water interface (Langmuir monolayer), both involving chiral 35 and non-chiral components 36,37 . Here we work with an azobenzene-based photoresponsive achiral amphiphile, Azo1 (see Methods), known to feature spontaneous chiral resolution.…”

Section: Resultsmentioning

confidence: 99%

Stirring competes with chemical induction in chiral selection of soft matter aggregates

et al. 2012

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“…This includes, in particular, the possibility that chiral layers are formed from achiral, racemic, and chiral species. [12][13][14][15] In some cases, indications of spontaneous chiral segregation of racemic films have been reported. [16][17][18][19] When the substrate atomic order is affected, even chiral restructuring may occur.…”

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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Spontaneous chiral symmetry breaking by achiral molecules in a Langmuir–Blodgett film

Cited by 167 publications

References 25 publications

Molecular chirality at surfaces

Molecular chirality at surfaces

Stirring competes with chemical induction in chiral selection of soft matter aggregates

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

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