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

4 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

ASJC Scopus subject areas

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

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    Gong, X., Zhou, J., Hartlieb, K. J., Miller, C., Li, P., Farha, O. K., Hupp, J. T., Young, R. M., Wasielewski, M. R., & 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