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 language | English (US) |
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Pages (from-to) | 6540-6544 |
Number of pages | 5 |
Journal | Journal of the American Chemical Society |
Volume | 140 |
Issue number | 21 |
DOIs | |
State | Published - May 30 2018 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 1819139: Experimental Crystal Structure Determination
Gong, X. (Creator), Zhou, J. (Creator), Hartlieb, K. J. (Creator), Miller, C. (Creator), Li, P. (Creator), Farha, O. K. (Creator), Hupp, J. T. (Creator), Young, R. M. (Creator), Wasielewski, M. R. (Creator) & Stoddart, J. F. (Creator), Cambridge Crystallographic Data Centre, 2018
DOI: 10.5517/ccdc.csd.cc1z1yxw, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1z1yxw&sid=DataCite
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