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Article: Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State

TitleDiscrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State
Authors
Issue Date2021
Citation
Journal of the American Chemical Society, 2021, v. 143, n. 1, p. 163-175 How to Cite?
AbstractThe solid-state properties of organic radicals depend on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4-dimethoxyphenylene), which associates in its bisradical dicationic redox state with the methyl viologen radical cation (MV•+) to give a 1:1 inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments reveal that the methoxy substituents on the p-phenylene linkers do not influence binding of the cyclophane toward small neutral guests - such as dimethoxybenzene and tetrathiafulvalene - whereas binding of larger radical cationic guests such as MV•+ by the reduced cyclophane decreases 10-fold. X-ray diffraction analysis reveals that the solid-state superstructure of the 1:1 complex constitutes a discrete entity with weak intermolecular orbital overlap between neighboring complexes. Transient nutation EPR experiments and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap, while the quartet-state spin configuration is higher in energy and inaccessible at ambient temperature. Superconducting quantum interference device (SQUID) measurements reveal that the trisradical tricationic complexes interact antiferromagnetically and form a one-dimensional Heisenberg antiferromagnetic chain along the a-axis of the crystal. These results offer insights into the design and synthesis of organic magnetic materials based on host-guest complexes.
Persistent Identifierhttp://hdl.handle.net/10722/333487
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorAnamimoghadam, Ommid-
dc.contributor.authorJones, Leighton O.-
dc.contributor.authorCooper, James A.-
dc.contributor.authorBeldjoudi, Yassine-
dc.contributor.authorNguyen, Minh T.-
dc.contributor.authorLiu, Wenqi-
dc.contributor.authorKrzyaniak, Matthew D.-
dc.contributor.authorPezzato, Cristian-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorPatel, Hasmukh A.-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorSchatz, George C.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:19:45Z-
dc.date.available2023-10-06T05:19:45Z-
dc.date.issued2021-
dc.identifier.citationJournal of the American Chemical Society, 2021, v. 143, n. 1, p. 163-175-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333487-
dc.description.abstractThe solid-state properties of organic radicals depend on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4-dimethoxyphenylene), which associates in its bisradical dicationic redox state with the methyl viologen radical cation (MV•+) to give a 1:1 inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments reveal that the methoxy substituents on the p-phenylene linkers do not influence binding of the cyclophane toward small neutral guests - such as dimethoxybenzene and tetrathiafulvalene - whereas binding of larger radical cationic guests such as MV•+ by the reduced cyclophane decreases 10-fold. X-ray diffraction analysis reveals that the solid-state superstructure of the 1:1 complex constitutes a discrete entity with weak intermolecular orbital overlap between neighboring complexes. Transient nutation EPR experiments and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap, while the quartet-state spin configuration is higher in energy and inaccessible at ambient temperature. Superconducting quantum interference device (SQUID) measurements reveal that the trisradical tricationic complexes interact antiferromagnetically and form a one-dimensional Heisenberg antiferromagnetic chain along the a-axis of the crystal. These results offer insights into the design and synthesis of organic magnetic materials based on host-guest complexes.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleDiscrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jacs.0c07148-
dc.identifier.pmid33347315-
dc.identifier.scopuseid_2-s2.0-85099090623-
dc.identifier.volume143-
dc.identifier.issue1-
dc.identifier.spage163-
dc.identifier.epage175-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000611083700025-

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