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Article: Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane

TitleTetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane
Authors
Issue Date2012
Citation
Journal of the American Chemical Society, 2012, v. 134, n. 46, p. 19136-19145 How to Cite?
AbstractThe electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4′-bis(hydroxymethyl)tetrathiafulvalene (OTTFO) and 4,4′-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO • and STTFS•. The redox behavior of the macrocyclic polyether has been investigated by electrochemical techniques and UV-vis and electron paramagnetic resonance (EPR) spectroscopies. The [2]catenane in which the macrocyclic polyether is mechanically interlocked with the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring has also been prepared using template-directed protocols. In the case of the [2]catenane, the formation of the TTF hetero radical dimer is prevented sterically by the CBPQT 4+ ring. After a one-electron oxidation, a 70:30 ratio of OTTFO • to STTFS• is present at equilibrium, and, as a result, two translational isomers of the [2]catenane associated with these electronically different isomeric states transpire. EPR titration spectroscopy and simulations reveal that the radical states of the two constitutionally different TTF units in the [2]catenane still experience long-range electronic intramolecular coupling interactions, despite the presence of the CBPQT 4+ ring, when one or both of them are oxidized to the radical cationic state. These findings in the case of both the free macrocyclic polyether and the [2]catenane have led to a deeper fundamental understanding of the mechanism of radical cation dimer formation between constitutionally different TTF units. © 2012 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/333007
ISSN
2021 Impact Factor: 16.383
2020 SCImago Journal Rankings: 7.115
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWang, Cheng-
dc.contributor.authorDyar, Scott M.-
dc.contributor.authorCao, Dennis-
dc.contributor.authorFahrenbach, Albert C.-
dc.contributor.authorHorwitz, Noah-
dc.contributor.authorColvin, Michael T.-
dc.contributor.authorCarmieli, Raanan-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorDey, Sanjeev K.-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:16:03Z-
dc.date.available2023-10-06T05:16:03Z-
dc.date.issued2012-
dc.identifier.citationJournal of the American Chemical Society, 2012, v. 134, n. 46, p. 19136-19145-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333007-
dc.description.abstractThe electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4′-bis(hydroxymethyl)tetrathiafulvalene (OTTFO) and 4,4′-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO • and STTFS•. The redox behavior of the macrocyclic polyether has been investigated by electrochemical techniques and UV-vis and electron paramagnetic resonance (EPR) spectroscopies. The [2]catenane in which the macrocyclic polyether is mechanically interlocked with the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring has also been prepared using template-directed protocols. In the case of the [2]catenane, the formation of the TTF hetero radical dimer is prevented sterically by the CBPQT 4+ ring. After a one-electron oxidation, a 70:30 ratio of OTTFO • to STTFS• is present at equilibrium, and, as a result, two translational isomers of the [2]catenane associated with these electronically different isomeric states transpire. EPR titration spectroscopy and simulations reveal that the radical states of the two constitutionally different TTF units in the [2]catenane still experience long-range electronic intramolecular coupling interactions, despite the presence of the CBPQT 4+ ring, when one or both of them are oxidized to the radical cationic state. These findings in the case of both the free macrocyclic polyether and the [2]catenane have led to a deeper fundamental understanding of the mechanism of radical cation dimer formation between constitutionally different TTF units. © 2012 American Chemical Society.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleTetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja307577t-
dc.identifier.scopuseid_2-s2.0-84869412858-
dc.identifier.volume134-
dc.identifier.issue46-
dc.identifier.spage19136-
dc.identifier.epage19145-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000311324900040-

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