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Article: Mechanical bonds and topological effects in radical dimer stabilization

TitleMechanical bonds and topological effects in radical dimer stabilization
Authors
Issue Date2014
Citation
Journal of the American Chemical Society, 2014, v. 136, n. 31, p. 11011-11026 How to Cite?
AbstractWhile mechanical bonding stabilizes tetrathiafulvalene (TTF) radical dimers, the question arises: what role does topology play in catenanes containing TTF units? Here, we report how topology, together with mechanical bonding, in isomeric [3]- and doubly interlocked [2]catenanes controls the formation of TTF radical dimers within their structural frameworks, including a ring-in-ring complex (formed between an organoplatinum square and a {2+2} macrocyclic polyether containing two 1,5-dioxynaphthalene (DNP) and two TTF units) that is topologically isomeric with the doubly interlocked [2]catenane. The separate TTF units in the two {1+1} macrocycles (each containing also one DNP unit) of the isomeric [3]catenane exhibit slightly different redox properties compared with those in the {2+2} macrocycle present in the [2]catenane, while comparison with its topological isomer reveals substantially different redox behavior. Although the stabilities of the mixed-valence (TTF2)•+ dimers are similar in the two catenanes, the radical cationic (TTF•+)2 dimer in the [2]catenane occurs only fleetingly compared with its prominent existence in the [3]catenane, while both dimers are absent altogether in the ring-in-ring complex. The electrochemical behavior of these three radically configurable isomers demonstrates that a fundamental relationship exists between topology and redox properties. © 2014 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/333088
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorFrasconi, Marco-
dc.contributor.authorKikuchi, Takashi-
dc.contributor.authorCao, Dennis-
dc.contributor.authorWu, Yilei-
dc.contributor.authorLiu, Wei Guang-
dc.contributor.authorDyar, Scott M.-
dc.contributor.authorBarin, Gokhan-
dc.contributor.authorSarjeant, Amy A.-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorCarmieli, Raanan-
dc.contributor.authorWang, Cheng-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorGoddard, William A.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:16:39Z-
dc.date.available2023-10-06T05:16:39Z-
dc.date.issued2014-
dc.identifier.citationJournal of the American Chemical Society, 2014, v. 136, n. 31, p. 11011-11026-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333088-
dc.description.abstractWhile mechanical bonding stabilizes tetrathiafulvalene (TTF) radical dimers, the question arises: what role does topology play in catenanes containing TTF units? Here, we report how topology, together with mechanical bonding, in isomeric [3]- and doubly interlocked [2]catenanes controls the formation of TTF radical dimers within their structural frameworks, including a ring-in-ring complex (formed between an organoplatinum square and a {2+2} macrocyclic polyether containing two 1,5-dioxynaphthalene (DNP) and two TTF units) that is topologically isomeric with the doubly interlocked [2]catenane. The separate TTF units in the two {1+1} macrocycles (each containing also one DNP unit) of the isomeric [3]catenane exhibit slightly different redox properties compared with those in the {2+2} macrocycle present in the [2]catenane, while comparison with its topological isomer reveals substantially different redox behavior. Although the stabilities of the mixed-valence (TTF<inf>2</inf>)<sup>•+</sup> dimers are similar in the two catenanes, the radical cationic (TTF<sup>•+</sup>)<inf>2</inf> dimer in the [2]catenane occurs only fleetingly compared with its prominent existence in the [3]catenane, while both dimers are absent altogether in the ring-in-ring complex. The electrochemical behavior of these three radically configurable isomers demonstrates that a fundamental relationship exists between topology and redox properties. © 2014 American Chemical Society.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleMechanical bonds and topological effects in radical dimer stabilization-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja504662a-
dc.identifier.pmid25010890-
dc.identifier.scopuseid_2-s2.0-84905713903-
dc.identifier.volume136-
dc.identifier.issue31-
dc.identifier.spage11011-
dc.identifier.epage11026-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000340079800037-

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