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Article: Radically Enhanced Dual Recognition

TitleRadically Enhanced Dual Recognition
Authors
Keywordsbinding stoichiometry
host-guest systems
molecular recognition
radical-pairing interactions
Issue Date2021
Citation
Angewandte Chemie - International Edition, 2021, v. 60, n. 48, p. 25454-25462 How to Cite?
AbstractComplexation between a viologen radical cation (V.+) and cyclobis(paraquat-p-phenylene) diradical dication (CBPQT2(.+)) has been investigated and utilized extensively in the construction of mechanically interlocked molecules (MIMs) and artificial molecular machines (AMMs). The selective recognition of a pair of V.+ using radical-pairing interactions, however, remains a formidable challenge. Herein, we report the efficient encapsulation of two methyl viologen radical cations (MV.+) in a size-matched bisradical dicationic host — namely, cyclobis(paraquat-2,6-naphthalene)2(.+), i.e., CBPQN2(.+). Central to this dual recognition process was the choice of 2,6-bismethylenenaphthalene linkers for incorporation into the bisradical dicationic host. They provide the space between the two bipyridinium radical cations in CBPQN2(.+) suitable for binding two MV.+ with relatively short (3.05–3.25 Å) radical-pairing distances. The size-matched bisradical dicationic host was found to exhibit highly selective and cooperative association with the two MV.+ in MeCN at room temperature. The formation of the tetrakisradical tetracationic inclusion complex — namely, [(MV)2⊂CBPQN]4(.+) – in MeCN was confirmed by VT 1H NMR, as well as by EPR spectroscopy. The solid-state superstructure of [(MV)2⊂CBPQN]4(.+) reveals an uneven distribution of the binding distances (3.05, 3.24, 3.05 Å) between the three different V.+, suggesting that localization of the radical-pairing interactions has a strong influence on the packing of the two MV.+ inside the bisradical dicationic host. Our findings constitute a rare example of binding two radical guests with high affinity and cooperativity using host-guest radical-pairing interactions. Moreover, they open up possibilities of harnessing the tetrakisradical tetracationic inclusion complex as a new, orthogonal and redox-switchable recognition motif for the construction of MIMs and AMMs.
Persistent Identifierhttp://hdl.handle.net/10722/327734
ISSN
2023 Impact Factor: 16.1
2023 SCImago Journal Rankings: 5.300
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChen, Xiao Yang-
dc.contributor.authorMao, Haochuan-
dc.contributor.authorFeng, Yuanning-
dc.contributor.authorCai, Kang-
dc.contributor.authorShen, Dengke-
dc.contributor.authorWu, Huang-
dc.contributor.authorZhang, Long-
dc.contributor.authorZhao, Xingang-
dc.contributor.authorChen, Hongliang-
dc.contributor.authorSong, Bo-
dc.contributor.authorJiao, Yang-
dc.contributor.authorWu, Yong-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-04-24T05:09:36Z-
dc.date.available2023-04-24T05:09:36Z-
dc.date.issued2021-
dc.identifier.citationAngewandte Chemie - International Edition, 2021, v. 60, n. 48, p. 25454-25462-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/327734-
dc.description.abstractComplexation between a viologen radical cation (V.+) and cyclobis(paraquat-p-phenylene) diradical dication (CBPQT2(.+)) has been investigated and utilized extensively in the construction of mechanically interlocked molecules (MIMs) and artificial molecular machines (AMMs). The selective recognition of a pair of V.+ using radical-pairing interactions, however, remains a formidable challenge. Herein, we report the efficient encapsulation of two methyl viologen radical cations (MV.+) in a size-matched bisradical dicationic host — namely, cyclobis(paraquat-2,6-naphthalene)2(.+), i.e., CBPQN2(.+). Central to this dual recognition process was the choice of 2,6-bismethylenenaphthalene linkers for incorporation into the bisradical dicationic host. They provide the space between the two bipyridinium radical cations in CBPQN2(.+) suitable for binding two MV.+ with relatively short (3.05–3.25 Å) radical-pairing distances. The size-matched bisradical dicationic host was found to exhibit highly selective and cooperative association with the two MV.+ in MeCN at room temperature. The formation of the tetrakisradical tetracationic inclusion complex — namely, [(MV)2⊂CBPQN]4(.+) – in MeCN was confirmed by VT 1H NMR, as well as by EPR spectroscopy. The solid-state superstructure of [(MV)2⊂CBPQN]4(.+) reveals an uneven distribution of the binding distances (3.05, 3.24, 3.05 Å) between the three different V.+, suggesting that localization of the radical-pairing interactions has a strong influence on the packing of the two MV.+ inside the bisradical dicationic host. Our findings constitute a rare example of binding two radical guests with high affinity and cooperativity using host-guest radical-pairing interactions. Moreover, they open up possibilities of harnessing the tetrakisradical tetracationic inclusion complex as a new, orthogonal and redox-switchable recognition motif for the construction of MIMs and AMMs.-
dc.languageeng-
dc.relation.ispartofAngewandte Chemie - International Edition-
dc.subjectbinding stoichiometry-
dc.subjecthost-guest systems-
dc.subjectmolecular recognition-
dc.subjectradical-pairing interactions-
dc.titleRadically Enhanced Dual Recognition-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/anie.202109647-
dc.identifier.pmid34342116-
dc.identifier.scopuseid_2-s2.0-85114353167-
dc.identifier.volume60-
dc.identifier.issue48-
dc.identifier.spage25454-
dc.identifier.epage25462-
dc.identifier.eissn1521-3773-
dc.identifier.isiWOS:000693238400001-

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