Imaging the Absolute Configuration of a Chiral Epoxide in the Gas Phase

Herwig, P.; Zawatzky, Kerstin; Grieser, M.; Heber, O.; Jordon-Thaden, Brandon; Krantz, Claude; Novotný, Oldřich; Repnow, R.; Schurig, Volker; Schwalm, D.; Vager, Z.; Wolf, A.; Trapp, Oliver; Kreckel, H.

doi:10.1126/science.1246549

Cited by 134 publications

(121 citation statements)

References 34 publications

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“…This might happen due to the nature of possibly involved different ionization processes in multiphoton excitation and ionization schemes or due to the contribution of different conformers [54] [see also comment to Eq. (8)]. …”

Section: Quantification Of Multiphoton Pecdmentioning

confidence: 99%

Photoelectron Circular Dichroism of Bicyclic Ketones from Multiphoton Ionization with Femtosecond Laser Pulses

et al. 2014

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Photoelectron circular dichroism (PECD) is a CD effect up to the ten-percent regime and shows contributions from higher-order Legendre polynomials when multiphoton ionization is compared to single-photon ionization. We give a full account of our experimental methodology for measuring the multiphoton PECD and derive quantitative measures that we apply on camphor, fenchone and norcamphor. Different modulations and amplitudes of the contributing Legendre polynomials are observed despite the similarity in chemical structure. In addition, we study PECD for elliptically polarized light employing tomographic reconstruction methods. Intensity studies reveal dissociative ionization as the origin of the observed PECD effect, whereas ionization of the intermediate resonance is dominating the signal. As a perspective, we suggest to make use of our tomographic data as an experimental basis for a complete photoionization experiment and give a prospect of PECD as an analytic tool.

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Section: Quantification Of Multiphoton Pecdmentioning

confidence: 99%

Photoelectron Circular Dichroism of Bicyclic Ketones from Multiphoton Ionization with Femtosecond Laser Pulses

et al. 2014

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“…All of these experiments have employed the Coulomb explosion coincidence momentum imaging technique16171819, in which all charged fragments that are created when the multiply charged parent ion breaks up (“ explodes ”) are measured in coincidence and their momentum vectors are used to extract information about the dynamical change in the geometry of the parent molecule. Recently, this technique was also used to separate two enantiomers in a racemic mixture of the chiral molecules CHIClF and CHBrClF by measuring five-fold coincidences after strong-field laser ionization2021, and the related beam-foil Coulomb explosion method was used to study the absolute configuration of trans-2,3-dideuterooxirane (C 2 H 2 D 2 O)22.…”

mentioning

confidence: 99%

Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging

Ablikim

Bomme

Xiong

et al. 2016

Sci Rep

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An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C2H2Br2). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model.

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“…Our technique offers a novel approach to absolute configuration assignment, which is model independent, as it is based on direct imaging of the molecular structure. The main implications of our result for the stereochemistry of chiral molecules have been discussed already in a general scientific magazine [11], and the synthesis of the chiral dideuterooxirane compound and its chemical correlation with glyceraldehyde have been detailed in Ref. [12].…”

Section: Introductionmentioning

confidence: 70%

“…We carried out Monte Carlo simulations of Coulomb explosion measurements of 2,3-dideuterooxirane, using the equilibrium distances between the atomic constituents as input parameters (for density functional calculations, see [11], Supplemental Material). The simulations are based on a well-established CEI code that includes multiple scattering and charge exchange inside the ∼ 50Å thin target foil [18,19].…”

Section: Simulating Cei Of Dideuterooxiranementioning

confidence: 99%

Absolute configuration assignment of a chiral molecule in the gas phase using foil-induced Coulomb explosion imaging

et al. 2014

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Chiral molecules exist in two configurations that are nonsuperposable mirror images of one another. The underlying molecular structure is referred to as the absolute configuration. In chiral environments, the handedness of molecules influences their chemical characteristics dramatically, and therefore the determination of absolute configurations is of fundamental interest in organic chemistry and biology. Commonly applied techniques to assign absolute configuration are anomalous single-crystal x-ray diffraction and vibrational circular dichroism. However, these techniques become increasingly more challenging when applied to molecules that are made out of light atoms exclusively. Furthermore, there is no established method to determine the absolute handedness of gas-phase molecules that are not optically active. In this work, we apply the foil-induced Coulomb explosion imaging technique to determine directly the absolute configuration of the chiral molecule trans-2,3-dideuterooxirane (C₂OD₂H₂) in the gas phase. The experiment leads to the definitive assignment of the (R,R) configuration to an enantio-selected dideuterooxirane sample with a statistical confidence of 5σ. As the handedness of trans-2,3-dideuterooxirane is unambiguously linked by chemical synthesis to the stereochemical key reference glyceraldehyde, our results provide an independent verification of the absolute configuration of the stereochemical reference standard

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Imaging the Absolute Configuration of a Chiral Epoxide in the Gas Phase

Cited by 134 publications

References 34 publications

Photoelectron Circular Dichroism of Bicyclic Ketones from Multiphoton Ionization with Femtosecond Laser Pulses

Photoelectron Circular Dichroism of Bicyclic Ketones from Multiphoton Ionization with Femtosecond Laser Pulses

Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging

Absolute configuration assignment of a chiral molecule in the gas phase using foil-induced Coulomb explosion imaging

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