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Highly stable tetrathiafulvalene radical dimers in [3]catenanes

Spruell, Jason M. and Coskun, Ali and Friedman, Douglas C. and Forgan, Ross S. and Sarjeant, Amy A. and Trabolsi, Ali and Fahrenbach, Albert C. and Barin, Gokhan and Paxton, Walter F. and Dey, Sanjeev K. and Olson, Mark A. and Benítez, Diego and Tkatchouk, Ekaterina and Colvin, Michael T. and Carmielli, Raanan and Caldwell, Stuart T. and Rosair, Georgina M. and Hewage, Shanika Gunatilaka and Duclairoir, Florence and Seymour, Jennifer L. and Slawin, Alexandra M. Z. and Goddard, William A., III and Wasielewski, Michael R. and Cooke, Graeme and Stoddart, J. Fraser (2010) Highly stable tetrathiafulvalene radical dimers in [3]catenanes. Nature Chemistry, 2 (10). pp. 870-879. ISSN 1755-4330.

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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.

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URLURL TypeDescription ReadCube access
Coskun, Ali0000-0002-4760-1546
Sarjeant, Amy A.0000-0002-1993-0406
Goddard, William A., III0000-0003-0097-5716
Wasielewski, Michael R.0000-0003-2920-5440
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2010 Macmillan Publishers Limited. Received 18 February 2010; accepted 14 June 2010; published online 25 July 2010. 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 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.
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)FA9550-07-1-0534
Department of Energy (DOE)DE-AC02-06CH11357
Michigan Economic Development CorporationUNSPECIFIED
Michigan Technology Tri-Corridor085P1000817
NSF Graduate Research FellowshipUNSPECIFIED
Northwestern UniversityUNSPECIFIED
Link FoundationUNSPECIFIED
Engineering and Physical Sciences Research Council (EPSRC)GR/M32702
Engineering and Physical Sciences Research Council (EPSRC)EP/E018211
Subject Keywords:Organic chemistry; Physical chemistry; Supramolecular chemistry
Issue or Number:10
Record Number:CaltechAUTHORS:20101012-101217044
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:20399
Deposited By: Jason Perez
Deposited On:05 Nov 2010 18:12
Last Modified:09 Mar 2020 13:19

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