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Article: Quantum Mechanical and Experimental Validation that Cyclobis(paraquat-p-phenylene) Forms a 1:1 Inclusion Complex with Tetrathiafulvalene

TitleQuantum Mechanical and Experimental Validation that Cyclobis(paraquat-p-phenylene) Forms a 1:1 Inclusion Complex with Tetrathiafulvalene
Authors
KeywordsDFT calculations
donor-acceptor systems
rotaxanes
tetrathiafulvalene
Issue Date2016
Citation
Chemistry - A European Journal, 2016, v. 22, n. 8, p. 2736-2745 How to Cite?
AbstractThe promiscuous encapsulation of π-electron-rich guests by the π-electron-deficient host, cyclobis(paraquat-p-phenylene) (CBPQT4+), involves the formation of 1:1 inclusion complexes. One of the most intensely investigated charge-transfer (CT) bands, assumed to result from inclusion of a guest molecule inside the cavity of CBPQT4+, is an emerald-green band associated with the complexation of tetrathiafulvalene (TTF) and its derivatives. This interpretation was called into question recently in this journal based on theoretical gas-phase calculations that reinterpreted this CT band in terms of an intermolecular side-on interaction of TTF with one of the bipyridinium (BIPY2+) units of CBPQT4+, rather than the encapsulation of TTF inside the cavity of CBPQT4+. We carried out DFT calculations, including solvation, that reveal conclusively that the CT band emerging upon mixing TTF with CBPQT4+ arises from the formation of a 1:1 inclusion complex. In support of this conclusion, we have performed additional experiments on a [2]rotaxane in which a TTF unit, located in the middle of its short dumbbell, is prevented sterically from interacting with either one of the two BIPY2+ units of a CBPQT4+ ring residing on a separate [2]rotaxane in a side-on fashion. This [2]rotaxane has similar UV/Vis and 1H NMR spectroscopic properties with those of 1:1 inclusion complexes of TTF and its derivatives with CBPQT4+. The [2]rotaxane exists as an equimolar mixture of cis- and trans-isomers associated with the disubstituted TTF unit in its dumbbell component. Solid-state structures were obtained for both isomers, validating the conclusion that the TTF unit, which gives rise to the CT band, resides inside CBPQT4+.
Persistent Identifierhttp://hdl.handle.net/10722/333160
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorHartlieb, Karel J.-
dc.contributor.authorLiu, Wei Guang-
dc.contributor.authorFahrenbach, Albert C.-
dc.contributor.authorBlackburn, Anthea K.-
dc.contributor.authorFrasconi, Marco-
dc.contributor.authorHafezi, Nema-
dc.contributor.authorDey, Sanjeev K.-
dc.contributor.authorSarjeant, Amy A.-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorGoddard, William A.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:17:11Z-
dc.date.available2023-10-06T05:17:11Z-
dc.date.issued2016-
dc.identifier.citationChemistry - A European Journal, 2016, v. 22, n. 8, p. 2736-2745-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/333160-
dc.description.abstractThe promiscuous encapsulation of π-electron-rich guests by the π-electron-deficient host, cyclobis(paraquat-p-phenylene) (CBPQT4+), involves the formation of 1:1 inclusion complexes. One of the most intensely investigated charge-transfer (CT) bands, assumed to result from inclusion of a guest molecule inside the cavity of CBPQT4+, is an emerald-green band associated with the complexation of tetrathiafulvalene (TTF) and its derivatives. This interpretation was called into question recently in this journal based on theoretical gas-phase calculations that reinterpreted this CT band in terms of an intermolecular side-on interaction of TTF with one of the bipyridinium (BIPY2+) units of CBPQT4+, rather than the encapsulation of TTF inside the cavity of CBPQT4+. We carried out DFT calculations, including solvation, that reveal conclusively that the CT band emerging upon mixing TTF with CBPQT4+ arises from the formation of a 1:1 inclusion complex. In support of this conclusion, we have performed additional experiments on a [2]rotaxane in which a TTF unit, located in the middle of its short dumbbell, is prevented sterically from interacting with either one of the two BIPY2+ units of a CBPQT4+ ring residing on a separate [2]rotaxane in a side-on fashion. This [2]rotaxane has similar UV/Vis and 1H NMR spectroscopic properties with those of 1:1 inclusion complexes of TTF and its derivatives with CBPQT4+. The [2]rotaxane exists as an equimolar mixture of cis- and trans-isomers associated with the disubstituted TTF unit in its dumbbell component. Solid-state structures were obtained for both isomers, validating the conclusion that the TTF unit, which gives rise to the CT band, resides inside CBPQT4+.-
dc.languageeng-
dc.relation.ispartofChemistry - A European Journal-
dc.subjectDFT calculations-
dc.subjectdonor-acceptor systems-
dc.subjectrotaxanes-
dc.subjecttetrathiafulvalene-
dc.titleQuantum Mechanical and Experimental Validation that Cyclobis(paraquat-p-phenylene) Forms a 1:1 Inclusion Complex with Tetrathiafulvalene-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.201502157-
dc.identifier.scopuseid_2-s2.0-84958156954-
dc.identifier.volume22-
dc.identifier.issue8-
dc.identifier.spage2736-
dc.identifier.epage2745-
dc.identifier.eissn1521-3765-
dc.identifier.isiWOS:000370193000023-

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