Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition

Xirui Gong, Jiawang Zhou, Karel J. Hartlieb, Claire Miller, Peng Li, Omar K. Farha, Joseph T Hupp, Ryan M. Young, Michael R Wasielewski, J. Fraser Stoddart

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

An octacationic diazaperopyrenium (DAPP2+)-based homo[2]catenane (DAPPHC8+), wherein no fewer than eight positive charges are associated within a mechanically interlocked molecule, has been produced in 30% yield under ambient conditions as a result of favorable homophilic interactions, reflecting a delicate balance between strong π- π interactions and the destabilizing penalty arising from Coulombic repulsions between DAPP2+ units. This DAPPHC8+ catenane is composed of two identical mechanically interlocked tetracationic cyclophanes, namely DAPPBox4+, each of which contains one DAPP2+ unit and one extended viologen (ExBIPY2+) unit, linked together by two p-xylylene bridges. The solid-state structure of the homo[2]catenane demonstrates how homophilic interactions play an important role in the formation of DAPPHC8+, in which the mean ring planes of the two DAPPBox4+ cyclophanes are oriented at about 60° with respect to each other, with a centroid-to-centroid separation of 3.7 Å between the mean planes of the outer ExBIPY2+ and inner DAPP2+ units, and 3.6 Å between the mean planes of the two inner DAPP2+ units. We show that irradiation of the DAPPHC8+ catenane at 330 nm in acetonitrile solution results in simultaneous energy and electron transfer. The latter occurs from the inner DAPP2+ dimer to the outer ExBIPY2+ unit, leading to the generation of a temporary charge-separated state within a rigid and robust homo[2]catenane. Compared to DAPPBox4+, both forward- and back-electron transfer in DAPPHC8+ occur with faster rates, owing to the closer proximity between the electron donor and acceptor in the homo[2]catenane than in the separated cyclophane.

Original languageEnglish
Pages (from-to)6540-6544
Number of pages5
JournalJournal of the American Chemical Society
Volume140
Issue number21
DOIs
Publication statusPublished - May 30 2018

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Hominidae
Electrons
Acetonitrile
Dimers
Viologens
Irradiation
Molecules
Energy Transfer
catenane

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Gong, X., Zhou, J., Hartlieb, K. J., Miller, C., Li, P., Farha, O. K., ... Stoddart, J. F. (2018). Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition. Journal of the American Chemical Society, 140(21), 6540-6544. https://doi.org/10.1021/jacs.8b03407

Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition. / Gong, Xirui; Zhou, Jiawang; Hartlieb, Karel J.; Miller, Claire; Li, Peng; Farha, Omar K.; Hupp, Joseph T; Young, Ryan M.; Wasielewski, Michael R; Stoddart, J. Fraser.

In: Journal of the American Chemical Society, Vol. 140, No. 21, 30.05.2018, p. 6540-6544.

Research output: Contribution to journalArticle

Gong, X, Zhou, J, Hartlieb, KJ, Miller, C, Li, P, Farha, OK, Hupp, JT, Young, RM, Wasielewski, MR & Stoddart, JF 2018, 'Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition', Journal of the American Chemical Society, vol. 140, no. 21, pp. 6540-6544. https://doi.org/10.1021/jacs.8b03407
Gong, Xirui ; Zhou, Jiawang ; Hartlieb, Karel J. ; Miller, Claire ; Li, Peng ; Farha, Omar K. ; Hupp, Joseph T ; Young, Ryan M. ; Wasielewski, Michael R ; Stoddart, J. Fraser. / Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 21. pp. 6540-6544.
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abstract = "An octacationic diazaperopyrenium (DAPP2+)-based homo[2]catenane (DAPPHC8+), wherein no fewer than eight positive charges are associated within a mechanically interlocked molecule, has been produced in 30{\%} yield under ambient conditions as a result of favorable homophilic interactions, reflecting a delicate balance between strong π- π interactions and the destabilizing penalty arising from Coulombic repulsions between DAPP2+ units. This DAPPHC8+ catenane is composed of two identical mechanically interlocked tetracationic cyclophanes, namely DAPPBox4+, each of which contains one DAPP2+ unit and one extended viologen (ExBIPY2+) unit, linked together by two p-xylylene bridges. The solid-state structure of the homo[2]catenane demonstrates how homophilic interactions play an important role in the formation of DAPPHC8+, in which the mean ring planes of the two DAPPBox4+ cyclophanes are oriented at about 60° with respect to each other, with a centroid-to-centroid separation of 3.7 {\AA} between the mean planes of the outer ExBIPY2+ and inner DAPP2+ units, and 3.6 {\AA} between the mean planes of the two inner DAPP2+ units. We show that irradiation of the DAPPHC8+ catenane at 330 nm in acetonitrile solution results in simultaneous energy and electron transfer. The latter occurs from the inner DAPP2+ dimer to the outer ExBIPY2+ unit, leading to the generation of a temporary charge-separated state within a rigid and robust homo[2]catenane. Compared to DAPPBox4+, both forward- and back-electron transfer in DAPPHC8+ occur with faster rates, owing to the closer proximity between the electron donor and acceptor in the homo[2]catenane than in the separated cyclophane.",
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