Abstract
Two [3]catenane ‘molecular flasks’ have been designed to create stabilized, redox-controlled tetrathiafulvalene (TTF) dimers, enabling their spectrophotometric and structural properties to be probed in detail. The mechanically interlocked framework of the [3]catenanes creates the ideal arrangement and ultrahigh local concentration for the encircled TTF units to form stable dimers associated with their discrete oxidation states. These dimerization events represent an affinity umpolung, wherein the inversion in electronic affinity replaces the traditional TTF-bipyridinium interaction, which is over-ridden by stabilizing mixed-valence (TTF)2•+ and radical-cation (TTF•+)2 states inside the ‘molecular flasks.’ The experimental data, collected in the solid state as well as in solution under ambient conditions, together with supporting quantum mechanical calculations, are consistent with the formation of stabilized paramagnetic mixed-valence dimers, and then diamagnetic radical-cation dimers following subsequent one-electron oxidations of the [3]catenanes.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Lewis, I. C. & Singer, L. J. Electron spin resonance of radical cations produced by oxidation of aromatic hydrocarbons with SbCl5 . J. Chem. Phys. 43, 2712–2727 (1965).
Torrance, J. B., Scott, B. A., Welber, B., Kaufman, F. B. & Seiden, P. E. Optical properties of the radical cation tetrathiafulvalenium (TTF+) in its mixed-valence and mono-valence halide salts. Phys. Rev. B 19, 730–741 (1979).
Bozio, R., Zanon, I., Girlando, A. & Pecile, C. Vibrational spectroscopy of molecular constitutents of one-dimensional organic conductors – tetrathiafulvalene (TTF), TTF+, and (TTF+)2 dimer. J. Chem. Phys. 71, 2282–2293 (1979).
Rosokha, S. V. & Kochi, J. K. Molecular and electronic structures of the long-bonded π-dimers of tetrathiafulvalene cation-radical in intermolecular electron transfer and in (solid-state) conductivity. J. Am. Chem. Soc. 129, 828–838 (2007).
Tanaka, K., Kunita, T., Ishiguro, F., Naka, K. & Chujo, Y. Modulation of morphology and conductivity of mixed-valence tetrathiafulvalene nanofibers by coexisting organic acid anions. Langmuir 25, 6929–6933 (2009).
Porter, W. W. & Vaid, T. P. Isolation and characterisation of phenyl viologen as a radical cation and neutral molecule. J. Org. Chem. 70, 5028–5035 (2005).
Khodorkovsky, V. et al. Do π-dimers of tetrathiafulvalene cation radicals really exist at room temperature? Chem. Commun. 2736–2737 (2001).
Sliwa, W., Bachowska, B. & Zelichowicz, N. Chemistry of viologens. Heterocycles 32, 2241–2273 (1991).
Monk, P. M. S. The Viologens: Physiochemical properties, synthesis and applications of the salts of 4,4′-bipyridine (John Wiley & Sons, 1998).
Kosower, E. M. & Cotter, J. L. Stable free radicals II. The reduction of 1 methyl 4-cyanopyridinium ion to methylviologen cation radical. J. Am. Chem. Soc. 86, 5524–5527 (1964).
Geuder, W., Hünig, S. & Suchy, A. Single and double bridged viologens and intramolecular pimerisation of their cation radicals. Tetrahedron 42, 1665–1677 (1986).
Evans, A. G., Evans, J. C. & Baker, M. W. Study of bipyridyl radical cations. Part 5. Effect of structure on the dimerisation equilibrium. J. Chem. Soc. Perkin Trans. 2, 1787–1789 (1977).
Claude-Montigny, B., Merlin, A. & Tondre, C. Microenvironment effects on the kinetics of electron-transfer reactions involving dithionite ions and viologens. 2. Stabilisation of ion radicals by polyelectrolytes and dimerisation kinetics of dialkyl viologens. J. Phys. Chem. 96, 4432–4437 (1992).
Meisel, D., Mulac, W. A. & Metheson, M. S. Catalysis of methyl viologen radical reactions by polymer-stabilised gold sols. J. Phys. Chem. 85, 179–187 (1981).
Furue, M. & Nozakura, S. Photoinduced 2-electron reduction of methyl viologen dimer by 2-propanol through intramolecular process and formation of viologen radical cation dimer. Chem. Lett. 9, 821–824 (1980).
Bendikov, M., Wudl, F. & Perepichka, D. F., Tetrathiafulvalenes, oligoacenes, and their buckminsterfullerene derivatives: the brick and mortar of organic electronics. Chem. Rev. 104, 4891–4945 (2004).
Canevet, D., Sallé, M., Zhang, G., Zhang, D. & Zhu, D. Tetrathiafulvalene (TTF) derivatives: key building-blocks for switchable processes. Chem. Commun. 2245–2269 (2009).
Jeon, W. S., Kim, H. J., Lee, C. & Kim, K. Control of the stoichiometry of host-guest complexation by redox chemistry of guests: inclusion of methylviologen in cucurbit[8]uril. Chem. Commun. 1828–1829 (2002).
Ziganshina, A. Y., Ko, Y. H., Jeon, W. S. & Kim, K. Stable π-dimer of a tetrathiafulvalene cation radical encapsulated in the cavity of cucurbit[8]uril. Chem. Commun. 806–807 (2004).
Yoshizawa, M., Kumazawa, K. & Fujita, M. Room-temperature and solution-state observation of the mixed-valence cation radical dimer of tetrathiafulvalene [(TTF)2]+•, within a self-assembled cage. J. Am. Chem. Soc. 127, 13456–13457 (2005).
Spanggaard, H. et al. Multiple-bridged bis-tetrathiafulvalene: new synthetic protocols and spectroelectrochemical investigations. J. Am. Chem. Soc. 122, 9486–9494 (2000).
Chiang, P. T., Chen, N. C., Lai, C. C. & Chiu, S. H. Direct observation of mixed-valence and radical cation dimer states of tetrathiafulvalene in solution at room temperature: association and disassociation of molecular clip dimers under oxidative control. Chem. Eur. J. 14, 6546–6552 (2008).
Lyskawa, J. et al. Monitoring the formation of TTF dimers by Na+ complexation. Chem. Commun. 2233–2235 (2006).
Lee, J. W. et al. Synthetic molecular machine based on reversible end-to-interior and end-to-end loop formation triggered by electrochemical stimuli. Chem. Asian J. 3, 1277–1283 (2008).
Trabolsi, A. et al. Redox-driven switching in pseudorotaxanes. New J. Chem. 33, 254–263 (2009).
Aprahamian, I., Olsen, J. C., Trabolsi, A. & Stoddart, J. F. Tetrathiafulvalene radical cation dimerisation in a bistable tripodal [4]rotaxane. Chem. Eur. J. 14, 3889–3895 (2008).
Hwang, I., Ziganshina, A. Y., Ko, Y. H., Yun, G. & Kim, K. A new three-way supramolecular switch based on redox-controlled interconversion of hetero- and homo guest pair inclusion inside a host molecule. Chem. Commun. 416–418 (2009).
Song, C. & Swager, T. M. π-Dimer formation as the driving force for calix[4]arene-based molecular actuators. Org. Lett. 10, 3575–3578 (2008).
Takita, R., Song, C. & Swager, T. M. π-Dimer formation in an oligothiophene tweezer molecule. Org. Lett. 10, 5003–5005 (2008).
Trabolsi, A. et al. Radically enhanced molecular recognition. Nature Chem. 2, 42–49 (2009).
Kim, K. et al. Functionalised cucurbiturils and their applications. Chem. Soc. Rev. 36, 267–279 (2007).
Seebach, D. Methods of reactivity umpolung. Angew. Chem. Int. Ed. Engl. 18, 239–258 (1979).
Sessler, J. L. et al. “Umpolung” photoinduced charge separation in an anion-bound supramolecular complex. J. Am. Chem. Soc. 130, 15256–15257 (2008).
Descalzo, A. B., Martínez-Máñez, R., Sancenón, F., Hoffmann, K. & Rurack, K. The supramolecular chemistry of organic-inorganic hybrid materials. Angew. Chem. Int. Ed. 45, 5924–5948 (2006).
Odell, B. et al. Cyclobis(paraquat-p-phenylene)—a tetracationic multipurpose receptor. Angew. Chem. Int. Ed. 27, 1547–1550 (1988).
Green, J. E. et al. A 160-kilobit molecular electronic memory patterned at 1011 bits per square centimetre. Nature 445, 414–417 (2007).
Liu, Y. et al. Linear artificial molecular muscles. J. Am. Chem. Soc. 127, 9745–9759 (2005).
Saha, S., Leung, K. C. F., Nguyen, T. D., Stoddart, J. F. & Zink, J. I. Nanovalves. Adv. Funct. Mater. 17, 685–693 (2007).
Asakawa, M. et al. Cyclobis(paraquat-4,4′-biphenylene) – an organic molecular square. Chem. Eur. J. 2, 877–893 (1996).
Spruell, J. M. et al. A push-button molecular switch. J. Am. Chem. Soc. 131, 11571–11580 (2009).
Dichtel, W. R. et al. Kinetic and thermodynamic approaches for the efficient formation of mechanical bonds. Acc. Chem. Res. 41, 1750–1761 (2008).
Miljanić, O. Š. et al. Structural and co-conformational effects of alkyne-derived subunits in charged donor-acceptor [2]catenanes. J. Am. Chem. Soc. 129, 8236–8246 (2007).
Eglinton, G. & Galbraith, A. R. Cyclic diynes. Chem. Ind. 737–738 (1956).
Siemsen, P., Livingston, R. C. & Diederich, F. Acetylenic coupling: a powerful tool in molecular construction. Angew. Chem. Int. Ed. 39, 2633–2657 (2000).
Ünsal, Ö. & Godt, A. Synthesis of a [2]catenane with functionalities and 87-membered rings. Chem. Eur. J. 5, 1728–1733 (1999).
Hamilton, D. G., Sanders, J. K. M., Davies, J. E., Clegg, W. & Teat, S. J. Neutral [2]catenanes from oxidative coupling of π-stacked components. Chem. Commun. 897–898 (1997).
Dietrich-Buchecker, C. O., Khémiss, A. & Sauvage, J. P. High-yield synthesis of multiring copper(I) catenates by acetylenic oxidative coupling. J. Chem. Soc. Chem. Commun. 1376–1378 (1986).
Gunter, M. J. & Farquhar, S. M. Neutral π-associated porphyrin [2]catenanes. Org. Biomol. Chem. 1, 3450–3457 (2003).
Sato, Y., Yamasaki, R. & Saito, S. Synthesis of [2]catenanes by oxidative intramolecular diyne coupling mediated by macrocyclic copper(I) complexes. Angew. Chem. Int. Ed. 48, 504–507 (2009).
Raymo, F. M., Bartberger, M. D., Houk, K. N. & Stoddart, J. F. The magnitude of [C–H···O] hydrogen bonding in molecular and supramolecular assemblies. J. Am. Chem. Soc. 123, 9264–9267 (2001).
Johnson, C. K. & Watson, C. R. Superstructure and modulation wave analysis for unidimensional conductor hepta(tetrathiafulvalene) pentaiodide. J. Chem. Phys. 64, 2271–2286 (1976).
Garcia-Yoldi, I., Miller, J. S. & Novoa, J. J. Theoretical study of the electronic structure of [tetrathiafulvalene]22+ dimers and their long, intradimer multicenter bonding in solution and the solid state. J. Phys. Chem. A 113, 484–492 (2009).
Connelly, N. G. & Geiger, W. E. Chemical redox agents for organometallic chemistry. Chem. Rev. 96, 877–910 (1996).
Zhao, Y. & Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theo. Chem. Acc. 120, 215–241 (2008).
Zhao, Y. & Truhlar, D. G. Density functionals with broad applicability in chemistry. Acc. Chem. Res. 41, 157–167 (2008).
Benítez, D., Tkatchouk, E., Yoon, I., Stoddart, J. F. & Goddard, W. A. III Experimentally-based recommendations of density functionals for predicting properties in mechanically interlocked molecules. J. Am. Chem. Soc. 130, 14928–14929 (2008).
Vácha, M., Půžová, T. & Kvíčalová, M. Radio frequency magnetic fields disrupt magnetoreception in American cockroach. J. Exp. Biol. 212, 3473–3477 (2009).
Acknowledgements
The authors acknowledge support from the Air Force Office of Scientific Research under the Multidisciplinary Research Program of the University Research Initiative (award number FA9550-07-1-0534, “Bioinspired Supramolecular Enzymatic Systems”) and the National Science Foundation under CHE-0924620. M.R.W. was supported by the National Science Foundation under Grant No. CHE-0718928. Proteomics and Informatic services were provided by the CBC-UIC Research Resources Center Proteomics and Informatics Services Facility, which was established by a grant from The Searle Funds at the Chicago Community Trust to the Chicago Biomedical Consortium. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Use of the LS-CAT Sector 21 was supported by the Michigan Economic Development Corporation and the Michigan Technology Tri-Corridor (Grant 085P1000817). J.M.S. acknowledges the National Science Foundation for a Graduate Research Fellowship and Northwestern University for a Presidential Fellowship. M.T.C. thanks the Link Foundation for a fellowship. G.C. thanks the EPSRC for support (GR/M32702, EP/E018211). G.C. thanks R. C. Hartley for his help regarding preliminary EPR measurements and Patrice Woisel for advice regarding the preliminary synthesis of cyclobis(paraquat-4,4′-biphenylene) and its complexation with TTF.
Author information
Authors and Affiliations
Contributions
J.M.S., A.C., G.C., and J.F.S. conceived the project and prepared the manuscript. J.M.S., A.C., G.B., and S.K.D. synthesized the different molecules studied in this work. R.S.F., A.A.S., M.A.O., and A.M.Z.S. were responsible for growing single-crystals and/or solving X-ray crystal structures. F.D., S.G.H., and S.T.C. were involved in the preliminary investigations of the complexation behaviour of 1 and TTF. G.M.R. was responsible for solving the X-ray structure of (TTF2 ⊂ 1). A.T. and A.C.F. were responsible for electrochemical studies. M.T.C., R.C., and M.R.W. were responsible for the EPR studies. J.L.S. was responsible for the mass spectrometry. D.C.F. was responsible for NMR investigations. D.B., E.T., and W.A.G.III performed DFT calculations. W.F.P. provided invaluable insights into the switching mechanisms.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 2101 kb)
Supplementary information
Crystallographic data for (TTF2⊂1)·4PF6 (CIF 51 kb)
Supplementary information
Crystallographic data for 2·4PF6·2.5MeCN (CIF 72 kb)
Supplementary information
Crystallographic data for 3·4PF6·3MeCN (CIF 35 kb)
Supplementary information
Crystallographic data for 3·4PF6·ClO4 (CIF 39 kb)
Supplementary information
Crystallographic data for 3·2PF6·4ClO4 (CIF 73 kb)
Rights and permissions
About this article
Cite this article
Spruell, J., Coskun, A., Friedman, D. et al. Highly stable tetrathiafulvalene radical dimers in [3]catenanes. Nature Chem 2, 870–879 (2010). https://doi.org/10.1038/nchem.749
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nchem.749
This article is cited by
-
Tetrathiafulvalenes as anchors for building highly conductive and mechanically tunable molecular junctions
Nature Communications (2022)
-
Overtemperature-protection intelligent molecular chiroptical photoswitches
Nature Communications (2021)
-
Radical-pairing-induced molecular assembly and motion
Nature Reviews Chemistry (2021)
-
Engineering interlocking DNA rings with weak physical interactions
Nature Communications (2014)
-
Redox-induced solid-solid state transformation of tetrathiafulvalene (TTF) microcrystals into mixed-valence and π-dimers in the presence of nitrate anions
Journal of Solid State Electrochemistry (2014)