Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published July 10, 2014 | Supplemental Material
Journal Article Open

Mechanical Bonds and Topological Effects in Radical Dimer Stabilization


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.

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).

Attached Files

Supplemental Material - ja504662a_si_001.pdf

Supplemental Material - ja504662a_si_002.cif

Supplemental Material - ja504662a_si_003.cif

Supplemental Material - ja504662a_si_004.cif

Supplemental Material - ja504662a_si_005.cif

Supplemental Material - ja504662a_si_006.cif

Supplemental Material - ja504662a_si_007.cif

Supplemental Material - ja504662a_si_008.cif


Files (18.1 MB)
Name Size Download all
495.9 kB Download
327.1 kB Download
3.4 MB Download
1.1 MB Download
482.2 kB Download
10.6 MB Preview Download
487.7 kB Download
1.1 MB Download

Additional details

August 20, 2023
October 17, 2023