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Mechanically Stabilized Tetrathiafulvalene Radical Dimers

Coskun, Ali and Spruell, Jason M. and Barin, Gokhan and Fahrenbach, Albert C. and Forgan, Ross S. and Colvin, Michale T. and Carmieli, Raanan and Benítez, Diego and Tkatchouk, Ekaterina and Friedman, Douglas C. and Sarjeant, Amy A. and Wasielewski, Michael R. and Goddard, William A., III and Stoddart, J. Fraser (2011) Mechanically Stabilized Tetrathiafulvalene Radical Dimers. Journal of the American Chemical Society, 133 (12). pp. 4538-4547. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20110705-135756894

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Abstract

Two donor−acceptor [3]catenanes—composed of a tetracationic molecular square, cyclobis(paraquat-4,4′-biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-electron rich components—have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called “molecular flask” under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes. By replacing the DNP station with a butadiyne group, the distribution of the TTF radical-cation dimer can be changed from 60% to 100%. These findings have been established by several techniques including cyclic voltammetry, spectroelectrochemistry and UV−vis−NIR and EPR spectroscopies, as well as with X-ray diffraction analysis which has provided a range of solid-state crystal structures. The experimental data are also supported by high-level DFT calculations. The results contribute significantly to our fundamental understanding of the interactions within the TTF radical dimers.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja110584cDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja110584cPublisherArticle
ORCID:
AuthorORCID
Sarjeant, Amy A.0000-0002-1993-0406
Goddard, William A., III0000-0003-0097-5716
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2011 American Chemical Society. Published In Issue March 30, 2011; Article ASAP March 02, 2011; Received: November 24, 2010. We (J.F.S. and co-workers) acknowledge support from the Air Force Office of Scientific Research (AFSOR) under the Multidisciplinary Research Program of the University Research Initiative (MURI) Award FA9550-07-1-0534 on “Bioinspired Supramolecular Enzymatic Systems” and the National Science Foundation (NSF) under the auspices of Award CHE-0924620. J.F.S. and W.A.G. acknowledge support by the Microelectronics Advanced Research Corporation (MARCO) and its Focus Center Research Program (FCRP) on Functional Engineered NanoArchitectonics (FENA). Computational facilities were funded by grants from ARO-DURIP and ONR-DURIP. M.R. W. acknowledges support by the National Science Foundation (NSF) under Grant CHE-1012378. R.C. was supported as part of the ANSER Center, an Energy Frontier Research Center (EPFRC) funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0001059. D.B., E.T., and W.A.C acknowledge support from the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under Award No. DE-PS-08GO98004P. G.B. was supported as part of the Non-Equilibrium Research Center (NERC), which is an Energy Fronties Research Center (EFRC) funded by the U.S.Department of Energy (DOE),Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0000989. M.T.C. thanks the Link Foundation for a fellowship. G.B. thanks the International Center for Diffraction Data for the award of a 2011 Ludo Frevel Crystallography Scholarship. J.M.S. and A.C.F. acknowledge the National Science Foundation (NSF) for a Graduate Research Fellowship and J.M.S. acknowledges Northwestern University for a Presidential Fellowship.
Funders:
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFSOR) Multidisciplinary Research Program of the University Research Initiative (MURI)FA9550-07-1-0534
NSFCHE-0924620
Microelectronics Advanced Research Corporation (MARCO) UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
NSFCHE-1012378
Department of Energy (DOE)DE-PS-08GO98004P
Department of Energy (DOE)DE-SC0000989
Link FoundationUNSPECIFIED
Ludo Frevel Crystallography ScholarshipUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Northwestern UniversityUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20110705-135756894
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110705-135756894
Official Citation:Mechanically Stabilized Tetrathiafulvalene Radical Dimers Ali Coskun, Jason M. Spruell, Gokhan Barin, Albert C. Fahrenbach, Ross S. Forgan, Michael T. Colvin, Raanan Carmieli, Diego Bentez, Ekaterina Tkatchouk, Douglas C. Friedman, Amy A. Sarjeant, Michael R. Wasielewski, William A. Goddard III, J. Fraser Stoddart Journal of the American Chemical Society 2011 133 (12), 4538-4547
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:24300
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:05 Jul 2011 21:36
Last Modified:03 Oct 2019 02:55

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