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Relative contractile motion of the rings in a switchable palindromic [3]rotaxane in aqueous solution driven by radical-pairing interactions

Leah S. Witus a, Karel J. Hartlieb a, Yuping Wang a, Aleksandrs Prokofjevs a, Marco Frasconi a, Jonathan C. Barnes ab, Edward J. Dale a, Albert C. Fahrenbach acd and J. Fraser Stoddart *a
aDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA. E-mail:
bDepartment of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA
cHoward Hughes Medical Institute, Department of Molecular Biology, and Center for Computational and Integrative Biology, Massachusetts General Hospital, Boston, Massachusetts 02114, USA
dEarth-Life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan

Received 13th June 2014 , Accepted 24th June 2014

First published on 10th July 2014

Artificial muscles are an essential component for the development of next-generation prosthetic devices, minimally invasive surgical tools, and robotics. This communication describes the design, synthesis, and characterisation of a mechanically interlocked molecule (MIM), capable of switchable and reversible linear molecular motion in aqueous solution that mimics muscular contraction and extension. Compatibility with aqueous solution was achieved in the doubly bistable palindromic [3]rotaxane design by using radical-based molecular recognition as the driving force to induce switching.

The concept of controlling molecular motion at will is an inspiring call to chemists.1 The design and synthesis of organic molecules that are capable of achieving movement is the first step towards translating that motion into a macroscopic effect through integration into larger systems.2 Some of the most impressive evidence that molecular motion can be translated into macroscopic motion comes from biology, wherein proteins and assemblies of proteins – themselves large molecules and supermolecules – routinely achieve incredible feats, from kinesin pulling organelles along microtubules, to the rotary motion of ATP synthase, to the propulsion that results from bacterial flagellum.3 When we turn to the synthetic world, there are still rather few comparable systems.4 One class of organic compounds is particularly well suited, however, to containing and exercising moving parts – namely, mechanically interlocked molecules5 (MIMs). Since MIMs consist of two or more components that cannot be separated without breaking a covalent bond, the bond(s) holding the molecule together is (are) called a mechanical bond. In the case of a rotaxane, a dumbbell-shaped component is encircled by a ring, and the inclusion of functional groups on the dumbbell, for which the ring has an affinity, provides recognition sites. When the affinity for one recognition site is increased or decreased relative to another one by a stimulus, this bistability serves as the driving force for the ring moving relative to the dumbbell. A unique interpretation of this design has been reported6 previously wherein the dumbbell contains two sets of identical recognition sites, in a constitutionally symmetric, or palindromic, design. Thus, in this prototypical design of a palindromic [3]rotaxane, the two rings achieve a linear contractile motion as they are switched between the inner and outer recognition sites.7 This motion (Fig. 1) mimics the molecular motion present in actin and myosin proteins within muscle tissue.3 In order to facilitate the next transition of the doubly bistable [3]rotaxane switches – from isolated molecules to integrated systems – and to enable biocompatible applications, these switches must operate in aqueous solution, the major medium of life itself.
image file: c4ob01228c-f1.tif
Fig. 1 (a) Graphical representation of the relative motion of the ring components, which undergo a redox-stimulated contraction and expansion in a doubly bistable palindromic [3]rotaxane. (b) The contraction of the sarcomere in biological muscle is achieved through the ATP-driven molecular motion of actin and myosin proteins sliding relative to each other.

Recently, we have discovered the potential of radical–radical pairing interactions8 in the context of MIMs. It has been found that 4,4′-bipyridinium (BIPY2+) units, upon reduction to their radical cationic state (BIPY+˙), form strong inclusion complexes with the reduced diradical, dicationic (CBPQT2(+˙)) form of cyclobis(paraquat-p-phenylene) (CBPQT4+). The radical-based pairing interaction in the reduced state is strong and represents the driving force for switching to the radical state co-conformation8d (RSCC) in a MIM, a process that is eliminated in the oxidised state by electrostatic repulsions between the positive charges on both components. Thus, redox stimuli initiate rapid and readily reversible switching, but what's more, this radical-based switching mechanism has been shown to occur in aqueous solution. Here, we incorporate this new switching mechanism into a palindromic [3]rotaxane.

The design of a doubly bistable palindromic [3]rotaxane requires two sets of identical recognition sites on the dumbbell. Our design utilises 1,5-dioxynaphthalene (DNP) units as the outer recognition sites, which enter into donor–acceptor interactions with the CBPQT4+ rings in the oxidised ground state co-conformation (GSCC). After reduction, the diradical, dicationic CBPQT2(+˙) ring has a strong preference for the inner BIPY+˙ recognition sites and a decreased affinity for the DNP units, resulting in a shuttling motion whose reversal is facilitated by the electrostatic repulsion between the positive charges on both the BIPY2+ units and the tetracationic ring upon re-oxidation.

The synthesis of the bistable palindromic [3]rotaxane was performed following the protocol outlined in Scheme 1. In order to achieve higher yields of the desired [3]rotaxane than had previously been possible with clipping-based rotaxanation approaches,6b we sought to use a threading-followed-by-stoppering protocol for the rotaxane formation. Therefore, the first step was synthesising an axle component, A·4PF6, with azide functionalities at each end to aid and abet the subsequent stoppering reaction. The synthesis of the axle begins with a DNP-tri(ethylene glycol) unit91 which was subjected to a monotosylation to induce desymmetrisation.10 The monotosylate 2 was reacted with sodium azide in order to install an azide group11 in 3. The remaining hydroxyl group on 3 was then tosylated in order to form 4 prior to its reaction with a bisviologen-based core125·2PF6 to form the axle A·4PF6.

image file: c4ob01228c-s1.tif
Scheme 1 Synthetic route to the palindromic [3]rotaxane 3R·12PF6 using a threading-followed-by-stoppering approach.

Rotaxanation was achieved by a threading-followed-by-stoppering approach wherein an excess of CBPQT·4PF6 was incubated with the axle in MeCN at room temperature for a week. An electron-deficient alkyne136 was added to form the stoppers as a result of copper-free Huigsen cycloadditions.14 The desired [3]rotaxane 3R·12PF6 was obtained in 46% yield, along with a small amount (8%) of a [2]rotaxane byproduct (2R·8PF6). See synthetic procedures in the ESI.

1H NMR spectroscopy of 3R·12PF6 confirmed the hypothesis that, in the non-reduced GSCC, the CBPQT4+ rings reside on the DNP recognition units. Fig. 2 shows partial 1H NMR spectra comparing the dumbbell D·4PF6, the [3]rotaxane 3R·12PF6 and the [2]rotaxane 2R·8PF6. An upfield shift was observed for the peaks corresponding to the DNP protons (labelled H4/8, H2/6, and H3/7) in the [2]- and [3]rotaxane, indicating that the DNP units are encircled by CBPQT4+ rings. This co-conformation was confirmed by through-space interactions observed in the 1H–1H ROESY NMR spectrum, shown in Fig. S9 in the ESI. Variable temperature 1H NMR spectra, which were recorded on the [2]rotaxane 2R·8PF6 demonstrate that, in the GSCC, the inner BIPY2+ recognition sites serve as electrostatic barriers preventing the shuttling of the ring from one DNP recognition site to the other. See Fig. S11 in the ESI.

image file: c4ob01228c-f2.tif
Fig. 2 Partial 1H NMR spectra (500 MHz, CD3CN, 298 K) comparing the dumbbell D·4PF6, the [2]rotaxane 2R·8PF6, and the [3]rotaxane 3R·12PF6 reveal upfield shifts of the resonances for the DNP protons in the rotaxanes (see Scheme 1 for proton labelling), indicating that the CBPQT4+ rings encircle the DNP units in the oxidised GSCC.

Following the characterisation of the [3]rotaxane 3R·12PF6, we were interested in investigating its switching properties, particularly in aqueous solution. The solubility of the [3]rotaxane can be modulated by counterion exchange, given the fact that the PF6 salt is highly soluble in organic solvents such as MeCN and Me2CO, and the Cl salt is soluble in aqueous solution. Counterion exchanges were achieved using NH4PF6 and nBu4NCl. The shuttling of the CBPQT4+ rings between the recognition sites, following reduction to the hexaradical hexacationic RSCC, was monitored electrochemically and also by UV-Vis-NIR spectroscopy since NMR characterisation of the paramagnetic species was not possible.

The reduction potential for 3R·12Cl in aqueous solution was determined (Fig. 3) by differential pulse voltammetry using Ag/AgCl as a reference. Compared to the free BIPY2+ units in the dumbbell structure (−615 mV) and in the ring (−410 mV), the reduction potential of the [3]rotaxane was significantly shifted (−368 mV). The shift of the BIPY+˙ signal in the [3]rotaxane toward more positive potential indicates the formation of the trisradical complex between the BIPY+˙ and CBPQT2(+˙). Spectroelectrochemistry (SEC) performed (Fig. 4) at an applied potential of −750 mV showed evidence for the shuttling of the reduced diradical, dicationic CBPQT2(+˙) rings from the DNP recognition sites to the inner BIPY+˙ sites. This was revealed by a change in the charge-transfer band corresponding to the interaction between the CBPQT4+ rings and the DNP units in the GSCC. A comparison of the spectra of the reduced [3]rotaxane species with those of the dumbbell D2(+·) and ring CBPQT2(+˙) in their reduced states showed an absorption band centred at 1125 nm characteristic of the trisradical interaction in the hexaradical, hexacationic [3]rotaxane 3R6(+·). SEC also showed significantly different absorption profiles for the reduced versus oxidised states of the [3]rotaxane. See Fig. S2 in the ESI. In addition to electrochemical stimuli, switching was also achieved by chemical means – Na2S2O4 and Zn dust for reduction in H2O and MeCN respectively, and O2 (air) for oxidation. See Fig. S3 and S4 in the ESI.

image file: c4ob01228c-f3.tif
Fig. 3 (a) Differential pulse voltammetry (DPV) of the [3]rotaxane 3R12+ (purple curve), dumbbell D4+ (red curve) and CBPQT4+ (blue curve) performed at 0.2 mM sample at 298 K in H2O–DMF (9[thin space (1/6-em)]:[thin space (1/6-em)]1, v/v) with 0.1 M KNO3 as the supporting electrolyte.

image file: c4ob01228c-f4.tif
Fig. 4 UV-Vis Spectra (60 μM, 298 K) of 3R6(+˙) (purple curve), D2(+˙) (red curve) and CBPQT2(+˙) (blue curve) conducted in H2O–DMF (9[thin space (1/6-em)]:[thin space (1/6-em)]1, v/v) with 0.1 M KNO3 as the supporting electrolyte at an applied potential of −750 mV vs. Ag/AgCl show different absorbances between species in their reduced states.

In summary, by combining new advances in radical-based MIM motifs with a design that results in relative contractile motion of the rings, we have produced a ‘next generation’ palindromic [3]rotaxane capable of redox switching in aqueous solution. The radical-pairing recognition motif is incredibly versatile, since it is amenable to switching by electrochemical or chemical stimuli in different media, including aqueous solution. This system brings the dream of artificial muscles that function employing the same mechanism natural muscle uses – namely molecular motion – one step closer.15 Operating in aqueous solution enables the integration of this molecular muscle mimic with biological interfaces. Future work will focus on the preparation of derivatives that include conjugation handles for incorporating this molecular switch into micro- and macroscopic materials and biological systems.


The research reported in this publication was supported by the National Institute of General Medical Sciences of the National Institutes of Health (NIH) under Award Number F32GM105403. The content is solely the responsibility of the authors and does not necessarily represent the official views of the NIH. This research is part (Project #34-949) of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) and Northwestern University (NU). The authors would like to thank both KACST and NU for their continued support of this research. A.C.F. was and E.J.D. is supported by the National Science Foundation (NSF) Graduate Research Fellowship Program. L.S.W. acknowledges support from the International Institute for Nanotechnology (IIN) at NU. J.C.B. was supported by a National Defense Science and Engineering Graduate Fellowship from the Department of Defense and gratefully acknowledges receipt of a Ryan Fellowship from the IIN while at NU.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c4ob01228c

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