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Electrochemically addressable trisradical rotaxanes organized within a metal–organic framework

McGonigal, P.R.; Deria, P.; Hod, I.; Moghadam, P.Z.; Avestro, A.-J.; Horwitz, N.E.; Gibbs-Hall, I.C.; Blackburn, A.K.; Chen, D.; Botros, Y.Y.; Wasielewski, M.R.; Snurr, R.Q.; Hupp, J.T.; Farha, O.K.; Stoddart, J.F.

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P. Deria

I. Hod

P.Z. Moghadam

N.E. Horwitz

I.C. Gibbs-Hall

A.K. Blackburn

D. Chen

Y.Y. Botros

M.R. Wasielewski

R.Q. Snurr

J.T. Hupp

O.K. Farha

J.F. Stoddart


The organization of trisradical rotaxanes within the channels of a Zr6-based metal–organic framework (NU-1000) has been achieved postsynthetically by solvent-assisted ligand incorporation. Robust ZrIV–carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. Ultraviolet–visible–near-infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR), and 1H nuclear magnetic resonance (NMR) spectroscopies all confirm the capture of redox-active rotaxanes within the mesoscale hexagonal channels of NU-1000. Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components can be accessed electrochemically in the solid state. In contradistinction to previous methods, this strategy for the incorporation of mechanically interlocked molecules within porous materials circumvents the need for de novo synthesis of a metal–organic framework, making it a particularly convenient approach for the design and creation of solid-state molecular switches and machines. The results presented here provide proof-of-concept for the application of postsynthetic transformations in the integration of dynamic molecular machines with robust porous frameworks.


McGonigal, P., Deria, P., Hod, I., Moghadam, P., Avestro, A., Horwitz, N., …Stoddart, J. (2015). Electrochemically addressable trisradical rotaxanes organized within a metal–organic framework. Proceedings of the National Academy of Sciences, 112(36), 11161-11168.

Journal Article Type Article
Acceptance Date Jul 23, 2015
Online Publication Date Aug 17, 2015
Publication Date Sep 8, 2015
Deposit Date Oct 14, 2015
Publicly Available Date Mar 8, 2016
Journal Proceedings of the National Academy of Sciences
Print ISSN 0027-8424
Electronic ISSN 1091-6490
Publisher National Academy of Sciences
Peer Reviewed Peer Reviewed
Volume 112
Issue 36
Pages 11161-11168
Keywords Mechanically interlocked molecules, Metal–organic framework, Molecular switches, Rotaxanes, Radicals.


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