Highly stable tetrathiafulvalene radical dimers in [3]catenanes

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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 overridden by stabilizing mixed-valence (TTF)(2)(center dot+) and radical-cation (TTF(center dot+))(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.
Publisher
NATURE PUBLISHING GROUP
Issue Date
2010-10
Language
English
Article Type
Article
Keywords

MIXED-VALENCE; DENSITY FUNCTIONALS; ROOM-TEMPERATURE; PI-DIMER; ELECTRON-TRANSFER; CATION RADICALS; SOLID-STATE; CHEMISTRY; DIMERIZATION; VIOLOGEN

Citation

NATURE CHEMISTRY, v.2, no.10, pp.870 - 879

ISSN
1755-4330
DOI
10.1038/NCHEM.749
URI
http://hdl.handle.net/10203/100932
Appears in Collection
EEW-Journal Papers(저널논문)
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