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Conformationally controlled chemistry

English title Conformationally controlled chemistry
Applicant Willitsch Stefan
Number 157874
Funding scheme SNSF Consolidator Grants
Research institution Physikalische Chemie Departement Chemie Universität Basel
Institution of higher education University of Basel - BS
Main discipline Physical Chemistry
Start/End 01.09.2015 - 30.11.2020
Approved amount 1'983'816.00
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Keywords (6)

conformers; cold ions; molecular beams; reaction dynamics; controlled chemistry; cold molecules

Lay Summary (German)

Lead
Das Verständnis des Zusammenhangs zwischen Struktur und chemischer Reaktivität von Molekülen ist eines der zentralen Aufgaben der Chemie. Viele Moleküle besitzen verschiedene Strukturen, die sich durch Rotation von Teilen des Moleküls um eine chemische Bindung ineinander umwandeln können (sog. Konformere). Im vorliegenden Projekt werden individuelle Konformere von komplexen Molekülen in der Gasphase isoliert und ihre chemische Reaktivität erstmals unter präzise kontrollierten Bedingungen untersucht.
Lay summary

Das Ziel des vorliegenden Projekts ist ein detailliertes Verständnis zwischen der Struktur eines Moleküls, insbesondere seiner Konformation, und seiner Reaktivität. Konformere sind die dominanten Isomere komplexer Moleküle und die Konformation eines Moleküls kann beträchtliche Auswirkungen auf seine chemische Reaktivität haben. Konformere wandeln sich jedoch oft durch ihre thermische Bewegung ineinander um und sind daher in der Regel sehr schwierig zu isolieren. Die präzisesten Bedingungen zur Untersuchung chemischer Reaktionen herrschen in der Gasphase vor, jedoch ist es bis vor kurzem nicht gelungen, einzelne Konformere unter diesen Bedingungen zu isolieren und gezielt zur Reaktion zu bringen.

Zusammen mit Partnern vom Deutschen Elektronen-Synchrotron (DESY) und der Universität Hamburg haben wir vor kurzem eine Methode entwickelt, um verschiedene Konformere eines Moleküls in der Gasphase durch elektrische Felder räumlich zu trennen und sie gezielt auf einen stationären Reaktionspartner zu lenken, um ihre chemische Reaktivität detailliert zu untersuchen. Im vorliegenden Projekt planen wir, diese Methode systematisch auf eine grössere Klasse von chemischen Prozessen zu erweitern und eine Reihe wichtiger chemischer Reaktionstypen hinsichtlich ihrer Konformerenselektivität in der Gasphase zu untersuchen. 

Wir erwarten, dass die Ergebnisse des Projekts neue Einsichten in grundlegende chemische Zusammenhänge und in die Mechanismen von chemischen Reaktionen liefern werden. Diese Erkenntnisse können u.a. für die synthetische Chemie und für das Verständnis der Chemie der Erdatmosphäre von Nutzen sein.

Direct link to Lay Summary Last update: 04.03.2015

Responsible applicant and co-applicants

Employees

Publications

Publication
Spatial Separation of the Conformers of Methyl Vinyl Ketone
Wang Jia, Kilaj Ardita, He Lanhai, Długołęcki Karol, Willitsch Stefan, Küpper Jochen (2020), Spatial Separation of the Conformers of Methyl Vinyl Ketone, in The Journal of Physical Chemistry A, 124(40), 8341-8345.
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
Rivero Uxía, Turan Haydar Taylan, Meuwly Markus, Willitsch Stefan (2020), 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, in Molecular Physics, e1825852-e1825852.
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
Kilaj Ardita, Gao Hong, Tahchieva Diana, Ramakrishnan Raghunathan, Bachmann Daniel, Gillingham Dennis, von Lilienfeld O. Anatole, Küpper Jochen, Willitsch Stefan (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, in Physical Chemistry Chemical Physics, 22(24), 13431-13439.
Observation of different reactivities of para and ortho-water towards trapped diazenylium ions
Kilaj Ardita, Gao Hong, Rösch Daniel, Rivero Uxia, Küpper Jochen, Willitsch Stefan (2018), Observation of different reactivities of para and ortho-water towards trapped diazenylium ions, in Nature Communications, 9(1), 2096-2096.
A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride
Rivero Uxía, Meuwly Markus, Willitsch Stefan (2017), A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride, in Chemical Physics Letters, 683, 598-605.
Physikalische Chemie 2016: Spektroskopie und Chemie mit kalten Ionen
Rösch Daniel, Willitsch Stefan (2017), Physikalische Chemie 2016: Spektroskopie und Chemie mit kalten Ionen, in Nachrichten aus der Chemie, 65(3), 326-329.
Chemistry with Controlled Ions
Willitsch S. (2017), Chemistry with Controlled Ions, in Stuart Rice Aaron Dinner (ed.), Wiley Interscience, Hoboken, 162, 307-307.
Ion Coulomb crystals: From quantum technology to chemistry close to the absolute zero point
Dulieu O., Willitsch S. (2017), Ion Coulomb crystals: From quantum technology to chemistry close to the absolute zero point, in Europhys. News, 48, 17-17.
Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry
Rösch D., Gao H., Kilaj A., Willitsch S. (2016), Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry, in Eur. Phys. J. Tech. Instr., 3, 044314-044314.
Cristaux coulombiens: De la technologie quantique à la chimie proche du zéro absolu
Dulieu O., Willitsch S. (2015), Cristaux coulombiens: De la technologie quantique à la chimie proche du zéro absolu, in Reflets Phys., 91, 44-44.

Collaboration

Group / person Country
Types of collaboration
Prof. Anatole von Lilienfeld, Universität Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Frank Stienkemeier, Albert-Ludwigs-Universität Freiburg Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Markus Meuwly, Universität Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. Jochen Küpper, DESY/Universität Hamburg Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Fall Meeting of the Swiss Chemical Society Poster Investigating state-specific effects in Penning ionization reactions 25.08.2020 Online, Switzerland Ploenes Ludger; Stranak Patrik;
XXII. Symposium on Atomic, Cluster and Surface Physics Poster New radical source for investigating conformational and state-specific effects in chemical reactions 02.02.2020 St. Moritz, Switzerland Stranak Patrik;
XXII. Symposium on Atomic, Cluster and Surface Physics Talk given at a conference Reaction kinetics of trapped molecular ions with conformer- and isomer-selected neutral molecules 02.02.2020 St. Moritz, Switzerland Kilaj Ardita;
27th Dynamics of Molecular Collisions (DMC) conference Talk given at a conference Reactive Atomistic Simulations of Diels-Alder Reactions: the Importance of Molecular Rotations 02.07.2019 Big Sky , United States of America Rivero Gonzalez Uxia;
27th Dynamics of Molecular Collisions (DMC) conference Poster Investigating conformational and state-specific effects in chemical reactions 02.07.2019 Big Sky, United States of America Ploenes Ludger;
Kolloquium des Fritz Haber Instituts der Max Planck Gesellschaft Individual talk New experiments with cold molecules and ions 14.06.2019 Berlin, Germany Willitsch Stefan;
New Horizons in Chemical Physics Talk given at a conference Cold molecular ions in traps: 
From cold chemistry to new spectroscopies 04.04.2019 Oxford, Great Britain and Northern Ireland Willitsch Stefan;
COST Action TIPICQA Kick-Off Meeting Talk given at a conference Cold molecular ion-neutral hybrid systems 06.03.2019 Granada, Spain Willitsch Stefan;
5. European Conference on Trapped Ions (ECTI) Talk given at a conference Complex ion-neutral hybrid systems 18.11.2018 Rehovot, Israel Willitsch Stefan;
Molecular Quantum Dynamics and Kinetics Talk given at a conference Studies of chemical kinetics and dynamics with cold and controlled molecules 08.10.2018 Athen, Greece Willitsch Stefan;
Fall Meeting of the Swiss Chemical Society Poster A study of the Diels-Alder reaction between 2,3-dibromo-1,3-butadiene and maleic anhydride 07.09.2018 Lausanne, Switzerland Rivero Gonzalez Uxia;
Stereodynamics 2018 Poster Investigating conformational and state-specific effects in chemical reactions 02.09.2018 Arosa, Switzerland Ploenes Ludger;
Stereodynamics 2018 Talk given at a conference Observation of different reactivities of para- and ortho-water towards trapped diazenylium ions 02.09.2018 Arosa, Switzerland Willitsch Stefan;
22nd European Conference on the Dynamics of Molecular Systems (MOLEC) Talk given at a conference Studies of chemical dynamics with cold and controlled molecules 26.08.2018 Dinard, France Willitsch Stefan;
22nd European Conference on the Dynamics of Molecular Systems (MOLEC) Poster Investigating conformational and state- specific effects in chemical reactions 26.08.2018 Dinard, France Stranak Patrik;
Conference on cold and controlled molecules and ions (CCMI) Talk given at a conference Observation of different reactivities of 
para- and ortho-water towards trapped diazenylium ions 25.03.2018 Athens, GA, United States of America Kilaj Ardita;
255th ACS National Meeting Talk given at a conference Probes of ion-neutral chemical dynamics 
with cold and controlled molecules 18.03.2018 New Orleans, United States of America Willitsch Stefan;
XXIst Symposium on Atomic, Cluster and Surface Physics Poster Investigating conformational effects in chemical reactions under single-collision conditions 11.02.2018 Obergurgl, Austria Ploenes Ludger;
XXIst Symposium on Atomic, Cluster and Surface Physics Poster Observation of different reactivities of para- and ortho- water towards cold diazenylium ions 11.02.2018 Obergurgl, Austria Kilaj Ardita;
AMO seminar, Weizmann Insititute of Science Individual talk Ion-neutral hybrid experiments 07.02.2018 Rehovot, Israel Willitsch Stefan;
SFB 1227 Kolloquium, Universität Hannover Individual talk New methods for probing the properties and dynamics of molecular quantum systems 25.01.2018 Hannover, Germany Willitsch Stefan;
IBER 2017 Talk given at a conference Ion-atom and ion-molecule hybrid experiments: From cold to controlled chemistry 12.09.2017 Barcelona, Spain Willitsch Stefan;
WATOC (11th trienial congress of the world association of theoretical and computational chemists) Poster A computational study of the Diels-Alder reaction between 2,3-dibromo-1,3-butadiene and maleic anhydride 27.08.2017 München, Germany Rivero Gonzalez Uxia;
SCS Fall Meeting 2017 Poster Conformational effects in radical reactions 21.08.2017 Bern, Switzerland Stranak Patrik;
53rd Symposium on Theoretical Chemistry Poster A computational study of the Diels-Alder reaction between 2,3-dibromo-1,3-butadiene and maleic anhydride 21.08.2017 Basel, Switzerland Rivero Gonzalez Uxia;
Swiss Chemical Society Fall Meeting 2017 Poster Mechanistic studies of conformationally controlled ionic cycloadditions and state-selected ion-molecule reactions 21.08.2017 Bern, Switzerland Kilaj Ardita;
26. Dynamics of Molecular Collisions Talk given at a conference Cold and controlled chemistry: 
 From small molecules to complex systems 09.07.2017 Granlibakken, United States of America Willitsch Stefan;
International Symposium on Molecular Beams Poster Conformation- and rotational-state-specific effects in gas-phase ion-molecule reactions 25.06.2017 Nijmegen, Netherlands Gao Hong;
27. International Symposium on Molecular Beams Talk given at a conference Cold and controlled ion-neutral reactions 25.06.2017 Nijmegen, Netherlands Willitsch Stefan;
Cold Molecular Ions Workshop Poster Mechanistic studies of conformationally controlled ionic cycloadditions and state-selected ion-molecule reactions 28.05.2017 Les Houches, France Kilaj Ardita;
Physik-Kolloquium, Universität Innsbruck Individual talk Cold Molecular Ions in Traps: From Precision Spectroscopy to Controlled Collisions 10.01.2017 Innsbruck, Austria Willitsch Stefan;
Aarhus Cold Molecules PhD School Individual talk Cold Molecular Ions: Methods and Applications 06.12.2016 Aarhus, Denmark Willitsch Stefan;
Stereodynamics 2016 Talk given at a conference New avenues for studies of chemical dynamics using cold and controlled molecules 06.11.2016 Taipei, Taiwan Willitsch Stefan;
EPFL Physical Chemistry Colloquium Individual talk Cold molecular ions in traps 29.09.2016 Lausanne, Switzerland Willitsch Stefan;
Swiss Chemical Society Fall Meeting 2016 Poster Cold and controlled mechanistic studies of conformer selected ionic cycloadditions 14.09.2016 Zürich, Switzerland Kilaj Ardita;
SCS fall meeting Poster Conformational effects in neutral and ionic Diels-Alder reactions 14.09.2016 Zürich, Switzerland Rivero Gonzalez Uxia;
XXI European Conference on the Dynamics of Molecular Systems Poster Conformation-specific effects in gas-phase neutral and ionic bimolecular chemical reactions 11.09.2016 Toledo, Spain Gao Hong;
252. National Meeting of the American Chemical Society Talk given at a conference AMO methods for precise studies of chemical reactions 21.08.2016 Philadelphia, United States of America Willitsch Stefan;
20. Symposium on Atomic, Surface and Cluster Physics Talk given at a conference Cold and controlled ion chemistry 07.02.2016 Davos, Switzerland Willitsch Stefan;
Swiss Snow Symposium Talk given at a conference Cold molecular ions in traps 22.01.2016 Saas-Fee, Switzerland Willitsch Stefan;
Colloquium, University of Warsaw Talk given at a conference Cold molecular ions in traps 17.12.2015 Warsaw, Poland Willitsch Stefan;


Self-organised

Title Date Place
4. European Conference on Trapped Ions 29.08.2016 Arosa, Switzerland

Associated projects

Number Title Start Funding scheme
140834 Ion-neutral chemistry in the sub-Kelvin regime 01.09.2012 SNSF Professorships
189907 Controlled reactive collisions with trapped ions 01.01.2020 COST (European Cooperation in Science and Technology)
156182 Hybrid trapping of cold molecules and cold ions 01.10.2014 Project funding
188329 Collisional and Half-Collisional Dynamics of Conformationally Selected Molecules 01.01.2020 South Korea

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 characterising 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 conformers 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.
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