Highly stable tetrathiafulvalene radical dimers in [3]catenanes

Jason M. Spruell, Ali Coskun, Douglas C. Friedman, Ross S. Forgan, Amy A. Sarjeant, Ali Trabolsi, Albert C. Fahrenbach, Gokhan Barin, Walter F. Paxton, Sanjeev K. Dey, Mark A. Olson, Diego Benitez, Ekaterina Tkatchouk, Michael T. Colvin, Raanan Carmielli, Stuart T. Caldwell, Georgina M. Rosair, Shanika Gunatilaka Hewage, Florence Duclairoir, Jennifer L. SeymourAlexandra Martha Zoya Slawin, William A. Goddard, Michael R. Wasielewski, Graeme Cooke, J. Fraser Stoddart

Research output: Contribution to journalArticlepeer-review

135 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)870-879
Number of pages10
JournalNature Chemistry
Volume2
Issue number10
Early online date25 Jul 2010
DOIs
Publication statusPublished - Oct 2010

Keywords

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

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