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Conformationally Controlled Chemistry
Third-party funded project
Project title Conformationally Controlled Chemistry
Principal Investigator(s) Willitsch, Stefan
Project Members Deb, Nabanita
Kilaj, Ardita
Rivero Gonzalez, Uxia Constanza
Stranak, Patrik
Rösch, Daniel
Gao, Hong
Ploenes, Ludger
Bachmann, Daniel
Organisation / Research unit Departement Chemie / Chemische Physik (Willitsch)
Project start 01.09.2015
Probable end 30.11.2020
Status Completed
Abstract

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.

Financed by Swiss National Science Foundation (SNSF)

Published results ()

  ID Autor(en) Titel ISSN / ISBN Erschienen in Art der Publikation
3720344  Rösch, Daniel; Gao, Hong; Kilaj, Ardita; Willitsch, Stefan  Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry  2195-7045  EPJ Techniques and Instrumentation  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
3728516  Rösch, Daniel  Reactive collisions with conformationally controlled molecules      Publication: Thesis (Dissertationen, Habilitationen) 
3932205  Rivero, Uxia; Meuwly, Markus; Willitsch, Stefan  A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride  0009-2614  Chemical Physics Letters  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
4496519  Kilaj, Ardita; Gao, Hong; Rösch, Daniel; Rivero, Uxia; Küpper, Jochen; Willitsch, Stefan  Observation of different reactivities of para and ortho-water towards trapped diazenylium ions  2041-1723  Nature Communications  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
4526113  Rivero, Uxia; Unke, Oliver T.; Meuwly, Markus; Willitsch, Stefan  Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations  0021-9606 ; 1089-7690  Journal of Chemical Physics  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
4600042  Kilaj, Ardita; Gao, Hong; Tahchieva, Diana; Ramakrishnan, Raghunathan; Bachmann, Daniel; Gillingham, Dennis; von Lilienfeld, O. Anatole; Kuepper, Jochen; Willitsch, Stefan  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  1463-9076 ; 1463-9084  Physical Chemistry Chemical Physics  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
4601337  Kilaj, Ardita; Gao, Hong; Tahchieva, Diana; Ramakrishnan, Raghunathan; Bachmann, Daniel; Gillingham, Dennis; von Lilienfeld, O. Anatole; Kuepper, Jochen; Willitsch, Stefan  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  1463-9076 eISSN: 1463-9084 cc-by  Physical chemistry chemical physics  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
4612906  Wang, Jia; Kilaj, Ardita; He, Lanhai; Dlugolecki, Karol; Willitsch, Stefan; Kuepper, Jochen  Spatial Separation of the Conformers of Methyl Vinyl Ketone  1089-5639  The journal of physical chemistry. A  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
4612910  Rivero, Uxia; Turan, Haydar Taylan; Meuwly, Markus; Willitsch, Stefan  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  0026-8976 ; 1362-3028  Molecular Physics  Publication: JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift) 
   

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