Shortcuts for Electron-Transfer through the Secondary Structure of Helical Oligo-1,2-Naphthylenes.

donor-acceptor systems electron transfer molecular electronics photochemistry time-resolved spectroscopy

Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
20 Dec 2019
Historique:
revised: 30 10 2019
received: 18 10 2019
pubmed: 2 11 2019
medline: 2 11 2019
entrez: 2 11 2019
Statut: ppublish

Résumé

Atropisomeric 1,2-naphthylene scaffolds provide access to donor-acceptor compounds with helical oligomer-based bridges, and transient absorption studies revealed a highly unusual dependence of the electron-transfer rate on oligomer length, which is due to their well-defined secondary structure. Close noncovalent intramolecular contacts enable shortcuts for electron transfer that would otherwise have to occur over longer distances along covalent pathways, reminiscent of the behavior seen for certain proteins. The simplistic picture of tube-like electron transfer can describe this superposition of different pathways including both the covalent helical backbone, as well as noncovalent contacts, contrasting the wire-like behavior reported many times before for more conventional molecular bridges. The exquisite control over the molecular architecture, achievable with the configurationally stable and topologically defined 1,2-naphthylene-based scaffolds, is of key importance for the tube-like electron transfer behavior. Our insights are relevant for the emerging field of multidimensional electron transfer and for possible future applications in molecular electronics.

Identifiants

pubmed: 31674695
doi: 10.1002/chem.201904771
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

16748-16754

Subventions

Organisme : Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
ID : 200021_178760
Organisme : Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
ID : BSSGI0-155902/1
Organisme : Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
ID : NCCR Molecular Systems Engineering

Informations de copyright

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Auteurs

Alessandro Castrogiovanni (A)

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

Patrick Herr (P)

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

Christopher B Larsen (CB)

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

Xingwei Guo (X)

Current address: Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, P.R. China.

Christof Sparr (C)

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

Oliver S Wenger (OS)

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

Classifications MeSH