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Issue 1, 2020
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Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

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Abstract

Although host–guest pairing interactions between bisradical dicationic cyclobis(paraquat-p-phenylene) (BB2(˙+)) and the bipyridinium radical cation (BIPY˙+) have been studied extensively, host molecules other than BB2(˙+) are few and far between. Herein, four bisradical dicationic cyclophanes with tunable cavity sizes are investigated as new bisradical dicationic hosts for accommodating the methyl viologen radical cation (MV˙+) to form trisradical tricationic complexes. The structure–property relationships between cavity sizes and binding affinities have been established by comprehensive solution and solid-state characterizations as well as DFT calculations. The association constants of the four new trisradical tricationic complexes are found to range between 7400 and 170 000 M−1, with the strongest one being 4.3 times higher than that for [MV⊂BB]3(˙+). The facile accessibility and tunable stability of these new trisradical tricationic complexes make them attractive redox-controlled recognition motifs for further use in supramolecular chemistry and mechanostereochemistry.

Graphical abstract: Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

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Supplementary files

Article information


Submitted
26 Sep 2019
Accepted
01 Nov 2019
First published
01 Nov 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 107-112
Article type
Edge Article

Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

K. Cai, Y. Shi, C. Cao, S. Vemuri, B. Cui, D. Shen, H. Wu, L. Zhang, Y. Qiu, H. Chen, Y. Jiao, C. L. Stern, F. M. Alsubaie, H. Xiao, J. Li and J. F. Stoddart, Chem. Sci., 2020, 11, 107
DOI: 10.1039/C9SC04860J

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