Second-harmonic generation circular-dichroism spectroscopy from chiral monolayers

Byers, J. A.; Yee, Herman I.; Petralli-Mallow, Teresa; Hicks, Janice M.

doi:10.1103/physrevb.49.14643

Cited by 176 publications

(159 citation statements)

References 11 publications

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“…[1][2][3][4][5][6][7][8][9] Recent investigations employing the scanning tunneling microscope revealed that this issue can be addressed successfully at the single molecule level with adsorbed species at solid surfaces. There are several aspects to chirality 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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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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“…2 In particular, when a chiral thin film or surface is illuminated by circularly polarized light, the intensity of the second-harmonic light generated can be different for left-and right-hand circularly polarized excitation. This and other chiral effects have been observed in secondharmonic generation from chiral monolayers adsorbed at an air/water interface or solid substrates, [3][4][5] and from Langmuir-Blodgett mono-and multilayers of chiral polymers. [6][7][8][9] These nonlinear optical-activity effects can occur in the electric-dipole approximation.…”

Section: ͓S0021-9606͑97͒52543-8͔mentioning

confidence: 99%

“…[6][7][8][9] These nonlinear optical-activity effects can occur in the electric-dipole approximation. 4,10 However, to properly explain the detailed experimental results for the case of Langmuir-Blodgett films of polyisocyanides, magnetic-dipole contributions to the nonlinearity must also be included. 11 To date, evidence of contributions beyond electric dipoles in second-harmonic generation from chiral thin films has only been obtained by a detailed comparison of several different second-harmonic signals.…”

Section: ͓S0021-9606͑97͒52543-8͔mentioning

confidence: 99%

Direct evidence of the failure of electric-dipole approximation in second-harmonic generation from a chiral polymer film

Elshocht

Verbiest

Kauranen

et al. 1997

The Journal of Chemical Physics

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“…One new approach to the study of surface chirality is second-order nonlinear optical spectroscopy methods such as Second Harmonic Generation (SHG), where the chiroptical effects are large and originate selectively from the interface where symmetry is broken (19) (20). New kinds of information can be obtained, for example, the spectrum of a unique chiral parameter characteristic of the molecule (χχγ2) can be measured (21).…”

mentioning

confidence: 99%

“…Enantiomeric excess at the interface can be measured (22). Absolute orientation of the molecules at the surface (pointed up or down) can be obtained if their chirality is known (19). It is possible to probe structural transitions in proteins as they adsorb to surfaces (23).…”

mentioning

confidence: 99%

The Physical Chemistry of Chirality

Hicks

2002

ACS Symposium Series

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Second-harmonic generation circular-dichroism spectroscopy from chiral monolayers

Cited by 176 publications

References 11 publications

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

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

Direct evidence of the failure of electric-dipole approximation in second-harmonic generation from a chiral polymer film

The Physical Chemistry of Chirality

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