Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 31, Pages 11011-11026Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja504662a
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Funding
- Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) [32-949]
- Northwestern University (NU)
- Non-Equilibrium Energy Research Center (NERC), which is an Energy Frontier Research Center (EFRC) - U.S. Department of Energy, Office of Basic Energy Sciences (DOE-BES) [DESC0000989]
- Japan Society for the Promotion of Science (JSPS)
- National Science Foundation (NSF)
- Northwestern University International Institute for Nanotechnology (IIN)
- U.S. NSF [CHE-1266201]
- Argonne-Northwestern Solar Energy Research (ANSER) Center, which is an Energy Frontier Research Center (EFRC) - U.S. Department of Energy, Office of Basic Energy Sciences (DOE-BES) [DE-SC0001059]
- [NSF-EFRI-1332411]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1266201] Funding Source: National Science Foundation
- Emerging Frontiers & Multidisciplinary Activities
- Directorate For Engineering [1332411] Funding Source: National Science Foundation
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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)(center dot+) dinners are similar in the two catenanes, the radical cationic (TTF center dot+)(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.
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