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Article: Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane

TitleIntramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane
Authors
Issue Date2017
Citation
Journal of the American Chemical Society, 2017, v. 139, n. 11, p. 4107-4116 How to Cite?
AbstractMolecules capable of performing highly efficient energy transfer and ultrafast photoinduced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photofunctional systems. Herein, we report on the synthesis, characterization, and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox4+, containing a diazaperopyrenium (DAPP2+) unit and an extended viologen (ExBIPY2+) unit, which are linked together by two p-xylylene bridges. Both1H NMR spectroscopy and single-crystal X-ray diffraction analysis confirm the formation of an asymmetric, rigid, box-like cyclophane, DAPPBox4+. The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif, leading to two types of π···π interactions: (i) between the ExBIPY2+ unit and the DAPP2+ unit (π···π distance of 3.7 Å) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY2+ unit (π···π distance of 3.2 Å) and phenylene ring in the closest orthogonal cyclophane. Moreover, the solution-phase photophysical properties of this cyclophane have been investigated by both steady-state and time-resolved absorption and emission spectroscopies. Upon photoexcitation of DAPPBox4+ at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the1*ExBIPY2+ unit to the DAPP2+ unit in 0.5 ps to yield1*DAPP2+. The same excitation wavelength simultaneously populates a higher excited state of1*DAPP2+ which then undergoes ultrafast intramolecular electron transfer from1*DAPP2+ to ExBIPY2+ to yield the DAPP3+•-ExBIPY+• radical ion pair in τ = 1.5 ps. Selective excitation of DAPP2+ at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.
Persistent Identifierhttp://hdl.handle.net/10722/333266
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorGong, Xirui-
dc.contributor.authorYoung, Ryan M.-
dc.contributor.authorHartlieb, Karel J.-
dc.contributor.authorMiller, Claire-
dc.contributor.authorWu, Yilei-
dc.contributor.authorXiao, Hai-
dc.contributor.authorLi, Peng-
dc.contributor.authorHafezi, Nema-
dc.contributor.authorZhou, Jiawang-
dc.contributor.authorMa, Lin-
dc.contributor.authorCheng, Tao-
dc.contributor.authorGoddard, William A.-
dc.contributor.authorFarha, Omar K.-
dc.contributor.authorHupp, Joseph T.-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:18:00Z-
dc.date.available2023-10-06T05:18:00Z-
dc.date.issued2017-
dc.identifier.citationJournal of the American Chemical Society, 2017, v. 139, n. 11, p. 4107-4116-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333266-
dc.description.abstractMolecules capable of performing highly efficient energy transfer and ultrafast photoinduced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photofunctional systems. Herein, we report on the synthesis, characterization, and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox4+, containing a diazaperopyrenium (DAPP2+) unit and an extended viologen (ExBIPY2+) unit, which are linked together by two p-xylylene bridges. Both1H NMR spectroscopy and single-crystal X-ray diffraction analysis confirm the formation of an asymmetric, rigid, box-like cyclophane, DAPPBox4+. The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif, leading to two types of π···π interactions: (i) between the ExBIPY2+ unit and the DAPP2+ unit (π···π distance of 3.7 Å) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY2+ unit (π···π distance of 3.2 Å) and phenylene ring in the closest orthogonal cyclophane. Moreover, the solution-phase photophysical properties of this cyclophane have been investigated by both steady-state and time-resolved absorption and emission spectroscopies. Upon photoexcitation of DAPPBox4+ at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the1*ExBIPY2+ unit to the DAPP2+ unit in 0.5 ps to yield1*DAPP2+. The same excitation wavelength simultaneously populates a higher excited state of1*DAPP2+ which then undergoes ultrafast intramolecular electron transfer from1*DAPP2+ to ExBIPY2+ to yield the DAPP3+•-ExBIPY+• radical ion pair in τ = 1.5 ps. Selective excitation of DAPP2+ at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleIntramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jacs.6b13223-
dc.identifier.pmid28225610-
dc.identifier.scopuseid_2-s2.0-85016158725-
dc.identifier.volume139-
dc.identifier.issue11-
dc.identifier.spage4107-
dc.identifier.epage4116-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000397477700029-

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