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Article: Electron delocalization in a rigid cofacial naphthalene-1,8:4,5- bis(dicarboximide) dimer

TitleElectron delocalization in a rigid cofacial naphthalene-1,8:4,5- bis(dicarboximide) dimer
Authors
Keywordscyclophane
excimer emission
mixed-valence compounds
radical anion dimer
π-electron delocalization
Issue Date2014
Citation
Angewandte Chemie - International Edition, 2014, v. 53, n. 36, p. 9476-9481 How to Cite?
AbstractInvestigating through-space electronic communication between discrete cofacially oriented aromatic π-systems is fundamental to understanding assemblies as diverse as double-stranded DNA, organic photovoltaics and thin-film transistors. A detailed understanding of the electronic interactions involved rests on making the appropriate molecular compounds with rigid covalent scaffolds and π-π distances in the range of ca. 3.5 Å. Reported herein is an enantiomeric pair of doubly-bridged naphthalene-1,8:4,5- bis(dicarboximide) (NDI) cyclophanes and the characterization of four of their electronic states, namely 1) the ground state, 2) the exciton coupled singlet excited state, 3) the radical anion with strong through-space interactions between the redox-active NDI molecules, and 4) the diamagnetic diradical dianion using UV/Vis/NIR, EPR and ENDOR spectroscopies in addition to X-ray crystallography. Despite the unfavorable Coulombic repulsion, the singlet diradical dianion dimer of NDI shows a more pronounced intramolecular π-π stacking interaction when compared with its neutral analog. Two are better than one: A doubly-bridged naphthalene diimide (NDI) cyclophane has been synthesized. It shows efficient π-orbital overlap between two rigid cofacial NDI units. The resulting through-space electronic delocalization in the neutral as well as reduced states induces emergent photophysical, electrochemical, and magnetic properties both in solution and in the solid phase. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/333091
ISSN
2023 Impact Factor: 16.1
2023 SCImago Journal Rankings: 5.300
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWu, Yilei-
dc.contributor.authorFrasconi, Marco-
dc.contributor.authorGardner, Daniel M.-
dc.contributor.authorMcGonigal, Paul R.-
dc.contributor.authorSchneebeli, Severin T.-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:16:40Z-
dc.date.available2023-10-06T05:16:40Z-
dc.date.issued2014-
dc.identifier.citationAngewandte Chemie - International Edition, 2014, v. 53, n. 36, p. 9476-9481-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/333091-
dc.description.abstractInvestigating through-space electronic communication between discrete cofacially oriented aromatic π-systems is fundamental to understanding assemblies as diverse as double-stranded DNA, organic photovoltaics and thin-film transistors. A detailed understanding of the electronic interactions involved rests on making the appropriate molecular compounds with rigid covalent scaffolds and π-π distances in the range of ca. 3.5 Å. Reported herein is an enantiomeric pair of doubly-bridged naphthalene-1,8:4,5- bis(dicarboximide) (NDI) cyclophanes and the characterization of four of their electronic states, namely 1) the ground state, 2) the exciton coupled singlet excited state, 3) the radical anion with strong through-space interactions between the redox-active NDI molecules, and 4) the diamagnetic diradical dianion using UV/Vis/NIR, EPR and ENDOR spectroscopies in addition to X-ray crystallography. Despite the unfavorable Coulombic repulsion, the singlet diradical dianion dimer of NDI shows a more pronounced intramolecular π-π stacking interaction when compared with its neutral analog. Two are better than one: A doubly-bridged naphthalene diimide (NDI) cyclophane has been synthesized. It shows efficient π-orbital overlap between two rigid cofacial NDI units. The resulting through-space electronic delocalization in the neutral as well as reduced states induces emergent photophysical, electrochemical, and magnetic properties both in solution and in the solid phase. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.-
dc.languageeng-
dc.relation.ispartofAngewandte Chemie - International Edition-
dc.subjectcyclophane-
dc.subjectexcimer emission-
dc.subjectmixed-valence compounds-
dc.subjectradical anion dimer-
dc.subjectπ-electron delocalization-
dc.titleElectron delocalization in a rigid cofacial naphthalene-1,8:4,5- bis(dicarboximide) dimer-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/anie.201403816-
dc.identifier.pmid25044761-
dc.identifier.scopuseid_2-s2.0-84906946218-
dc.identifier.volume53-
dc.identifier.issue36-
dc.identifier.spage9476-
dc.identifier.epage9481-
dc.identifier.eissn1521-3773-
dc.identifier.isiWOS:000342677000009-

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