Conformationally Controlled Chemistry

Research Project
|
01.09.2015
- 30.11.2020

The relationship between structure and reactivity is one of the central tenets of chemistry. In particular, many molecules exhibit structural isomers that interconvert over low barriers through rotations about covalent bonds (conformers). Conformers are the dominant isomers of complex molecules, and the conformation of a molecule can have pronounced effects on its chemical reactivity. Despite the eminent importance of conformational isomers in chemistry, very few studies have been reported thus far charac- terising conformational effects in chemical reactions under single-collision conditions. Consequently, the role of molecular conformations in fundamental reactions is only poorly understood. This striking lack of data reflects the experimental challenges to isolate und control specific conformers. In a recent proof-of-principle study [ Science 342 (2013), 98], we have spatially separated specific con- formers in a molecular beam through electrostatic deflection and directed them at a spatially localized reaction target of cold ions in a trap. This approach allowed us to study conformation-specific effects in ion-molecule reactions under precisely controlled experimental conditions in the gas phase. Here, we pro- pose a wide-ranging research programme aiming at extending our method to neutral reactions and applying it to a range of chemically relevant problems in order to explore the relationship between structure and reactivity in unprecedented detail. These methodological advances will enable for the first time detailed and systematic studies of the reaction mechanisms and dynamics of isolated conformers. The fundamental mechanistic insights gained will benefit a wide range of fields as diverse as fundamental reaction dynamics, organic synthesis, catalysis, atmospheric chemistry and rational molecule design.

Funding

Conformationally Controlled Chemistry

SNF Projekt (GrantsTool), 03.2015-02.2020 (60)

PI : Willitsch, Stefan.

Publications

Rivero, Uxia et al. (2021) ‘Reactive atomistic simulations of Diels-Alder-type reactions: conformational and dynamic effects in the polar cycloaddition of 2,3-dibromobutadiene radical ions with maleic anhydride’, Molecular Physics, 119(1-2), p. e1825852. Available at: https://doi.org/10.1080/00268976.2020.1825852.

URLs

Kilaj, Ardita et al. (2020) ‘Quantum-chemistry-aided identification, synthesis and experimental validation of model systems for conformationally controlled reaction studies: separation of the conformers of 2,3-dibromobuta-1,3-diene in the gas phase’, Physical Chemistry Chemical Physics, 22(24), pp. 13431–13439. Available at: https://doi.org/10.1039/d0cp01396j.

URLs

Wang, Jia et al. (2020) ‘Spatial Separation of the Conformers of Methyl Vinyl Ketone’, The journal of physical chemistry. A, 124(40), pp. 8341–8345. Available at: https://doi.org/10.1021/acs.jpca.0c05893.

URLs

Rivero, Uxia et al. (2019) ‘Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations’, Journal of Chemical Physics, 151(10), p. 104301. Available at: https://doi.org/10.1063/1.5114981.

URLs

Kilaj, Ardita et al. (2018) ‘Observation of different reactivities of para and ortho-water towards trapped diazenylium ions’, Nature Communications, 9(1), p. 2096. Available at: https://doi.org/10.1038/s41467-018-04483-3.

URLs

Rivero, Uxia, Meuwly, Markus and Willitsch, Stefan (2017) ‘A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride’, Chemical Physics Letters, 683, pp. 598–605. Available at: https://doi.org/10.1016/j.cplett.2017.03.063.

URLs

Rösch, Daniel et al. (2016) ‘Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry’, EPJ Techniques and Instrumentation, 3, p. 5. Available at: https://doi.org/10.1140/epjti/s40485-016-0032-3.

URLs

Conformationally Controlled Chemistry

Research Project
|
01.09.2015
- 30.11.2020

Funding

Conformationally Controlled Chemistry

SNF Projekt (GrantsTool), 03.2015-02.2020 (60)

PI : Willitsch, Stefan.

Publications

Wang, Jia et al. (2020) ‘Spatial Separation of the Conformers of Methyl Vinyl Ketone’, The journal of physical chemistry. A, 124(40), pp. 8341–8345. Available at: https://doi.org/10.1021/acs.jpca.0c05893.

Rivero, Uxia et al. (2019) ‘Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations’, Journal of Chemical Physics, 151(10), p. 104301. Available at: https://doi.org/10.1063/1.5114981.

Kilaj, Ardita et al. (2018) ‘Observation of different reactivities of para and ortho-water towards trapped diazenylium ions’, Nature Communications, 9(1), p. 2096. Available at: https://doi.org/10.1038/s41467-018-04483-3.

Rivero, Uxia, Meuwly, Markus and Willitsch, Stefan (2017) ‘A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride’, Chemical Physics Letters, 683, pp. 598–605. Available at: https://doi.org/10.1016/j.cplett.2017.03.063.

Rösch, Daniel et al. (2016) ‘Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry’, EPJ Techniques and Instrumentation, 3, p. 5. Available at: https://doi.org/10.1140/epjti/s40485-016-0032-3.

Members (9)

Stefan Willitsch

Principal Investigator

Ardita Kilaj

Project Member

Daniel Bachmann

Project Member

Daniel Rösch

Project Member

Hong Gao

Project Member

Ludger Ploenes

Project Member

Research Groups

Cold and Controlled Molecules

Conformationally Controlled Chemistry

Research Project | 01.09.2015 - 30.11.2020

Funding

Conformationally Controlled Chemistry

SNF Projekt (GrantsTool), 03.2015-02.2020 (60)

PI : Willitsch, Stefan.

Publications

Wang, Jia et al. (2020) ‘Spatial Separation of the Conformers of Methyl Vinyl Ketone’, The journal of physical chemistry. A, 124(40), pp. 8341–8345. Available at: https://doi.org/10.1021/acs.jpca.0c05893.

Rivero, Uxia et al. (2019) ‘Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations’, Journal of Chemical Physics, 151(10), p. 104301. Available at: https://doi.org/10.1063/1.5114981.

Kilaj, Ardita et al. (2018) ‘Observation of different reactivities of para and ortho-water towards trapped diazenylium ions’, Nature Communications, 9(1), p. 2096. Available at: https://doi.org/10.1038/s41467-018-04483-3.

Rivero, Uxia, Meuwly, Markus and Willitsch, Stefan (2017) ‘A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride’, Chemical Physics Letters, 683, pp. 598–605. Available at: https://doi.org/10.1016/j.cplett.2017.03.063.

Rösch, Daniel et al. (2016) ‘Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry’, EPJ Techniques and Instrumentation, 3, p. 5. Available at: https://doi.org/10.1140/epjti/s40485-016-0032-3.

Members (9)

Stefan Willitsch

Principal Investigator

Ardita Kilaj

Project Member

Daniel Bachmann

Project Member

Daniel Rösch

Project Member

Hong Gao

Project Member

Ludger Ploenes

Project Member

Research Groups

Cold and Controlled Molecules

Research Project
|
01.09.2015
- 30.11.2020