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Switching with orthogonal stimuli electrochemical ring-closure and photochemical ring-opening of bis(thiazolyl) maleimides

  • The photochemistry as well as electrochemistry of novel donor-acceptor bis(morpholinothiazolyl)maleimides has been investigated. Proper substitution of these diarylethene-type molecular switches leads to the unique situation in which their ring-closure can only be accomplished electrochemically, while ring-opening can only be achieved photochemically. Hence, these switches operate with orthogonal stimuli, i.e. redox potential and light, respectively. The switch system could be optimized by introducing trifluoromethyl groups at the reactive carbon atoms in order to avoid by-product formation during oxidative ring closure. Both photochemical and electrochemical pathways were investigated for methylated, trifluoromethylated, and nonsymmetrical bis(morpholinothiazolyl) maleimides as well as the bis(morpholinothiazolyl) cyclopentene reference compound. With the aid of the nonsymmetrical "mixed" derivative, the mechanism of electrochemically driven ring closure could be elucidated and seems to proceed via a dicationic intermediate generatedThe photochemistry as well as electrochemistry of novel donor-acceptor bis(morpholinothiazolyl)maleimides has been investigated. Proper substitution of these diarylethene-type molecular switches leads to the unique situation in which their ring-closure can only be accomplished electrochemically, while ring-opening can only be achieved photochemically. Hence, these switches operate with orthogonal stimuli, i.e. redox potential and light, respectively. The switch system could be optimized by introducing trifluoromethyl groups at the reactive carbon atoms in order to avoid by-product formation during oxidative ring closure. Both photochemical and electrochemical pathways were investigated for methylated, trifluoromethylated, and nonsymmetrical bis(morpholinothiazolyl) maleimides as well as the bis(morpholinothiazolyl) cyclopentene reference compound. With the aid of the nonsymmetrical "mixed" derivative, the mechanism of electrochemically driven ring closure could be elucidated and seems to proceed via a dicationic intermediate generated by two-fold oxidation. All experimental work has been complemented by density functional theory that provides detailed insights into the thermodynamics of the ring-open and closed forms, the nature of their excited states, and the reactivity of their neutral as well as ionized species in different electronic configurations. The particular diarylethene systems described herein could serve in multifunctional (logic) devices operated by different stimuli (inputs) and may pave the way to converting light into electrical energy via photoinduced "pumping" of redox-active meta-stable states.show moreshow less

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Metadaten
Author:Martin Herder, Manuel Utecht, Nicole Manicke, Lutz Grubert, Michael Pätzel, Peter SaalfrankORCiDGND, Stefan Hecht
DOI:https://doi.org/10.1039/c2sc21681g
ISSN:2041-6520 (print)
Parent Title (English):Chemical science
Publisher:Royal Society of Chemistry
Place of publication:Cambridge
Document Type:Article
Language:English
Year of first Publication:2013
Year of Completion:2013
Release Date:2017/03/26
Volume:4
Issue:3
Pagenumber:13
First Page:1028
Last Page:1040
Funder:German Research Foundation (DFG) [SFB 658, B8, C2]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert