Abstract
We report the encapsulation of free-base and zinc porphyrins by a tricyclic cyclophane receptor with subnanomolar binding affinities in water. The high affinities are sustained by the hydrophobic effect and multiple [CH···π] interactions covering large [π···π] stacking surfaces between the substrate porphyrins and the receptor. We discovered two co-conformational isomers of the 1:1 complex, where the porphyrin is orientated differently inside the binding cavity of the receptor on account of its tricyclic nature. The photophysical properties and chemical reactivities of the encapsulated porphyrins are modulated to a considerable extent by the receptor. Improved fluorescence quantum yields, red-shifted absorptions and emissions, and nearly quantitative energy transfer processes highlight the emergent photophysical enhancements. The encapsulated porphyrins enjoy unprecedented chemical stabilities, where their D/H exchange, protonation, and solvolysis under extremely acidic conditions are completely blocked. We anticipate that the ultrahigh stabilities and improved optical properties of these encapsulated porphyrins will find applications in single-molecule materials, artificial photodevices, and biomedical appliances.
Original language | English (US) |
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Pages (from-to) | 8938-8945 |
Number of pages | 8 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 19 |
DOIs | |
State | Published - May 13 2020 |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 1985129: Experimental Crystal Structure Determination
Liu, W. (Contributor), Lin, C. (Contributor), Weber, J. A. (Contributor), Stern, C. L. (Contributor), Young, R. M. (Contributor), Wasielewski, M. R. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24mpfx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24mpfx&sid=DataCite
Dataset
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CCDC 1985128: Experimental Crystal Structure Determination
Liu, W. (Contributor), Lin, C. (Contributor), Weber, J. A. (Contributor), Stern, C. L. (Contributor), Young, R. M. (Contributor), Wasielewski, M. R. (Contributor) & Stoddart, J. F. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24mpdw, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24mpdw&sid=DataCite
Dataset