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A computational study of potential molecular switches that exploit Baird's rule on excited-state aromaticity and antiaromaticity
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
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2014 (English)In: Faraday discussions (Online), ISSN 1359-6640, E-ISSN 1364-5498, Vol. 174, 105-124 p.Article in journal (Refereed) Published
Abstract [en]

A series of tentative single-molecule conductance switches which could be triggered by light were examined by computational means using density functional theory (DFT) with non-equilibrium Green's functions (NEGF). The switches exploit the reversal in electron counting rules for aromaticity and antiaromaticity upon excitation from the electronic ground state (S0) to the lowest [small pi][small pi]* excited singlet and triplet states (S1 or T1), as described by Huckel's and Baird's rules, respectively. Four different switches and one antifuse were designed which rely on various photoreactions that either lead from the OFF to the ON states (switches 1, 2 and 4, and antifuse 5) or from the ON to the OFF state (switch 3). The highest and lowest ideal calculated switching ratios are 1175 and 5, respectively, observed for switches 1 and 4. Increased thermal stability of the 1-ON isomer is achieved by benzannulation (switch 1B-OFF/ON). The effects of constrained electrode-electrode distances on activation energies for thermal hydrogen back-transfer from 1-ON to 1-OFF and the relative energies of 1-ON and 1-OFF at constrained geometries were also studied. The switching ratio is strongly distance-dependent as revealed for 1B-ON/OFF where it equals 711 and 148 when the ON and OFF isomers are calculated in electrode gaps with distances confined to either that of the OFF isomer or to that of the ON isomer, respectively.

Place, publisher, year, edition, pages
2014. Vol. 174, 105-124 p.
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-238681DOI: 10.1039/C4FD00084FISI: 000348331600007OAI: oai:DiVA.org:uu-238681DiVA: diva2:771847
Available from: 2014-12-15 Created: 2014-12-15 Last updated: 2017-12-05Bibliographically approved

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Löfås, HenrikWärnå, JohnEmanuelsson, RikardAhuja, RajeevGrigoriev, AntonOttosson, Henrik

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Materials TheoryDepartment of Chemistry - BMCPhysical Organic Chemistry
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