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Radically enhanced molecular recognition

Nature Chemistry volume 2, pages 42–49 (2010)Cite this article

Abstract

The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host–guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication.

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Figure 1: Formation of the inclusion complex and structural formulae and graphical representations.
Figure 2: Cyclic voltammetry (CV) showing evidence for formation of the inclusion complex.
Figure 3: Spectroelectrochemistry (SEC) of the model compounds V2+, SV2+ and CBPQT4+, and of equimolar mixtures of V2+ and CBPQT4+ and SV2+ and CBPQT4+ before (base line separation) and after reduction.
Figure 4: Graphical representations of the molecular orbital calculations.
Figure 5: Summary of the binding energy determination.
Figure 6: The stepwise synthesis of the three [2]rotaxanes 16+, 26+, and 36+.
Figure 7: Steady-state CW EPR spectroscopy.
Figure 8: Switching in an orthogonal manner.

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Acknowledgements

The research was supported by the US Air Force Office of Scientific Research (AFOSR) under their Multidisciplinary University Research Initiative (MURI), award number FA9550-07-1-0534 and by the US National Science Foundation (NSF) under grant numbers CHE-0718928 (M.R.W.) and CHE-0924620 (J.F.S.). M.T.C thanks the Link Foundation for a fellowship. MSC facilities were funded by grants from ARO-DURIP and ONR-DURIP.

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  1. Ali Trabolsi, Niveen Khashab & Hussam A. Khatib

    Present address: Present address: King Abdullah University of Science and Technology (KAUST), Thuwal, Saudia Arabia,

Authors and Affiliations

  1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, 60208, Illinois, USA

    Ali Trabolsi, Niveen Khashab, Albert C. Fahrenbach, Douglas C. Friedman, Karla K. Cotí, John-Carl Olsen, Matthew E. Belowich, Hussam A. Khatib & J. Fraser Stoddart

  2. Department of Chemistry, Argonne-Northwestern Solar Energy Research (ANSER) Center, and International Institute for Nanotechnology, Northwestern University,

    Michael T. Colvin, Raanan Carmielli & Michael R. Wasielewski

  3. Department of Chemistry and Biochemistry, University of California, Los Angeles, 90095, California, USA

    Karla K. Cotí & John-Carl Olsen

  4. Materials and Process Simulation Center, California Institute of Technology, Pasadena, 91125, California, USA

    Diego Benítez, Ekaterina Tkatchouk & William A. Goddard III

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Contributions

A.T. and J.F.S. conceived the project and prepared the manuscript. A.T., A.C.F., N.M.K., K.C. and M.E.B. synthesized the different molecules studied in this work. A.C.F. was responsible for electrochemical and spectroelectrochemical studies and the determination of the binding energy. D.C.F. performed the NMR spectroscopic studies. J.C.O. performed preliminary force-field simulations. D.B., E.T., and W.A.G.III performed DFT calculations. M.T.C., R.C., and M.R.W. performed all the EPR measurements. H.A.K. provided all the graphical representations used in this manuscript.

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Correspondence to J. Fraser Stoddart.

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Trabolsi, A., Khashab, N., Fahrenbach, A. et al. Radically enhanced molecular recognition. Nature Chem 2, 42–49 (2010). https://doi.org/10.1038/nchem.479

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