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Computational design of faster rotating second-generation light-driven molecular motors by control of steric effects
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Chemistry. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Chemistry. Linköping University, Faculty of Science & Engineering. Jining University, Peoples R China.
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Chemistry. Linköping University, Faculty of Science & Engineering.
2015 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 17, no 33, 21740-21751 p.Article in journal (Refereed) Published
Abstract [en]

We report a systematic computational investigation of the possibility to accelerate the rate-limiting thermal isomerizations of the rotary cycles of synthetic light-driven overcrowded alkene-based molecular motors through modulation of steric interactions. Choosing as a reference system a second-generation motor known to accomplish rotary motion in the MHz regime and using density functional theory methods, we propose a three-step mechanism for the thermal isomerizations of this motor and show that variation of the steric bulkiness of the substituent at the stereocenter can reduce the (already small) free-energy barrier of the rate-determining step by a further 15-17 kJ mol(-1). This finding holds promise for future motors of this kind to reach beyond the MHz regime. Furthermore, we demonstrate and explain why one particular step is kinetically favored by decreasing and another step is kinetically favored by increasing the steric bulkiness of this substituent, and identify a possible back reaction capable of impeding the rotary rate.

Place, publisher, year, edition, pages
Royal Society of Chemistry , 2015. Vol. 17, no 33, 21740-21751 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:liu:diva-121153DOI: 10.1039/c5cp02303cISI: 000359596600080PubMedID: 26234787OAI: oai:DiVA.org:liu-121153DiVA: diva2:852225
Note

Funding Agencies|Linkoping University; Swedish Research Council; Olle Engkvist Foundation; Wenner-Gren Foundations; NSFC [11404141]; National Supercomputer Centre (NSC) in Linkoping

Available from: 2015-09-08 Created: 2015-09-08 Last updated: 2017-12-04
In thesis
1. Computational Design of Molecular Motors and Excited-State Studies of Organic Chromophores
Open this publication in new window or tab >>Computational Design of Molecular Motors and Excited-State Studies of Organic Chromophores
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis presents computational quantum chemical studies of molecular motors and excited electronic states of organic chromophores.

The first and major part of the thesis is concerned with the design of light-driven rotary molecular motors. These are molecules that absorb light energy and convert it into 360° unidirectional rotary motion around a double bond connecting two molecular halves. In order to facilitate potential applications of molecular motors in nanotechnology, such as in molecular transport or in development of materials with photo-controllable properties, it is critical to optimize the rates and efficiencies of the chemical reactions that produce the rotary motion. To this end, computational methods are in this thesis used to study two different classes of molecular motors.

The first class encompasses the sterically overcrowded alkenes developed by Ben Feringa, co-recipient of the 2016 Nobel Prize in Chemistry. The rotary cycles of these motors involve two photoisomerization and two thermal isomerization steps, where the latter are the ones that limit the attainable rotational frequencies. In the thesis, several new motors of this type are proposed by identifying steric, electronic and conformational approaches to accelerate the thermal isomerizations. The second class contains motors that incorporate a protonated Schiff base and are capable to achieve higher photoisomerization rates than overcrowded alkene-based motors. In the thesis, a new motor of this type is proposed that produces unidirectional rotary motion by means of two photochemical steps alone. Also, this motor lacks both a stereocenter and helical motifs, which are key features of almost all synthetic rotary motors developed to date.

The second part of the thesis focuses on the design and assessment of composite computational procedures for modeling excited electronic states of organic chromophores. In particular, emphasis is put on developing procedures that facilitate the calculations of accurate 0−0 excitation energies of such compounds in a cost-effective way by combining quantum chemical methods with different accuracies.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2016. 64 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1794
National Category
Theoretical Chemistry Organic Chemistry Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-132611 (URN)10.3384/diss.diva-132611 (DOI)9789176856741 (ISBN)
Public defence
2016-12-15, Schrödinger (E324), Fysikhuset, Campus Valla, Linköping, 13:15 (English)
Opponent
Supervisors
Available from: 2016-11-16 Created: 2016-11-16 Last updated: 2016-11-17Bibliographically approved

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