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Mechanical Bonds and Topological Effects in Radical Dimer Stabilization

Frasconi, Marco and Kikuchi, Takashi and Cao, Dennis and Wu, Yilei and Liu, Wei-Guang and Dyar, Scott M. and Barin, Gokhan and Sarjeant, Amy A. and Stern, Charlotte L. and Carmieli, Raanan and Wang, Cheng and Wasielewski, Michael R. and Goddard, William A., III and Stoddart, J. Fraser (2014) Mechanical Bonds and Topological Effects in Radical Dimer Stabilization. Journal of the American Chemical Society, 136 (31). pp. 11011-11026. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20140904-120900207

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Abstract

While mechanical bonding stabilizes tetrathiafulvalene (TTF) radical dimers, the question arises: what role does topology play in catenanes containing TTF units? Here, we report how topology, together with mechanical bonding, in isomeric [3]- and doubly interlocked [2]catenanes controls the formation of TTF radical dimers within their structural frameworks, including a ring-in-ring complex (formed between an organoplatinum square and a {2+2} macrocyclic polyether containing two 1,5-dioxynaphthalene (DNP) and two TTF units) that is topologically isomeric with the doubly interlocked [2]catenane. The separate TTF units in the two {1+1} macrocycles (each containing also one DNP unit) of the isomeric [3]catenane exhibit slightly different redox properties compared with those in the {2+2} macrocycle present in the [2]catenane, while comparison with its topological isomer reveals substantially different redox behavior. Although the stabilities of the mixed-valence (TTF2)^(•+) dimers are similar in the two catenanes, the radical cationic (TTF^(•+))_2 dimer in the [2]catenane occurs only fleetingly compared with its prominent existence in the [3]catenane, while both dimers are absent altogether in the ring-in-ring complex. The electrochemical behavior of these three radically configurable isomers demonstrates that a fundamental relationship exists between topology and redox properties.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://pubs.acs.org/doi/abs/10.1021/ja504662aPublisherArticle
http://dx.doi.org/10.1021/ja504662aDOIArticle
http://pubs.acs.org/doi/suppl/10.1021/ja504662aRelated ItemSupporting Information
ORCID:
AuthorORCID
Frasconi, Marco0000-0003-2010-175X
Wu, Yilei0000-0001-6756-1855
Liu, Wei-Guang0000-0002-6633-7795
Sarjeant, Amy A.0000-0002-1993-0406
Goddard, William A., III0000-0003-0097-5716
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2014 American Chemical Society. Received: May 9, 2014. Publication Date (Web): July 10, 2014. We thank Professor Jean-Pierre Sauvage (University of Strasbourg, France) for fruitful discussions. This research is part (Project 32-949) 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 thank both KACST and NU for their continued support of this research. M.F. was supported by the Non-Equilibrium Energy Research Center (NERC), which is an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Basic Energy Sciences (DOE-BES), under Award DESC0000989. T.K. acknowledges the Japan Society for the Promotion of Science (JSPS) for the granting of a postdoctoral fellowship to carry out research abroad. D.C. is funded by a National Science Foundation (NSF) Graduate Research Fellowship and also acknowledges additional support from a Ryan Fellowship awarded by the Northwestern University International Institute for Nanotechnology (IIN). W.G.L. and W.A.G. were partially supported by NSF-EFRI-1332411. M.R.W. and S.M.D. are supported by the U.S. NSF under Grant No. CHE-1266201. R.C. is funded by the Argonne-Northwestern Solar Energy Research (ANSER) Center, which is an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Basic Energy Sciences (DOE-BES), under Award DE-SC0001059 (EPR Spectroscopy).
Funders:
Funding AgencyGrant Number
King Abdul-Aziz City for Science and Technology (KACST)UNSPECIFIED
Department of Energy (DOE)DE-SC0000989
NSF Graduate Research FellowshipUNSPECIFIED
Northwestern UniversityUNSPECIFIED
NSFEFMA-1332411
NSFCHE-1266201
Argonne-Northwestern Solar Energy ResearchUNSPECIFIED
Department of Energy (DOE)DE-SC0001059
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
Issue or Number:31
Record Number:CaltechAUTHORS:20140904-120900207
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140904-120900207
Official Citation:Mechanical Bonds and Topological Effects in Radical Dimer Stabilization Marco Frasconi, Takashi Kikuchi, Dennis Cao, Yilei Wu, Wei-Guang Liu, Scott M. Dyar, Gokhan Barin, Amy A. Sarjeant, Charlotte L. Stern, Raanan Carmieli, Cheng Wang, Michael R. Wasielewski, William A. Goddard III, and J. Fraser Stoddart Journal of the American Chemical Society 2014 136 (31), 11011-11026
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:49243
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:05 Sep 2014 23:25
Last Modified:03 Oct 2019 07:12

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