Multistate Switches: Ruthenium Alkynyl-Dihydroazulene/Vinylheptafulvene Conjugates.

Autor: Vlasceanu A; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Andersen CL; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Parker CR; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Hammerich O; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Morsing TJ; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Jevric M; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Lindbaek Broman S; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Kadziola A; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark., Nielsen MB; Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark. mbn@chem.ku.dk.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2016 May 23; Vol. 22 (22), pp. 7514-23. Date of Electronic Publication: 2016 Apr 26.
DOI: 10.1002/chem.201600178
Abstrakt: Multimode molecular switches incorporating distinct and independently addressable functional components have potential applications as advanced switches and logic gates for molecular electronics and memory storage devices. Herein, we describe the synthesis and characterization of four switches based on the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermoswitch pair functionalized with the ruthenium-based Cp*(dppe)Ru ([Ru*]) metal complex (dppe=1,2-bis(diphenylphosphino)ethane; Cp*=pentamethylcyclopentadienyl). The [Ru*]-DHA conjugates can potentially exist in six different states accessible by alternation between DHA/VHF, Ru(II) /Ru(III) , and alkynyl/vinylidene, which can be individually stimulated by using light/heat, oxidation/reduction, and acid/base. Access to the full range of states was found to be strongly dependent on the electronic communication between the metal center and the organic photoswitch in these [Ru*]-DHA conjugates. Detailed electrochemical, spectroscopic (UV/Vis, IR, NMR), and X-ray crystallographic studies indeed reveal significant electronic interactions between the two moieties. When in direct conjugation, the ruthenium metal center was found to quench the photochemical ring-opening of DHA, which in one case could be restored by protonation or oxidation, allowing conversion to the VHF state.
(© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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