TY - JOUR
T1 - Highly stable tetrathiafulvalene radical dimers in [3]catenanes
AU - Spruell, Jason M.
AU - Coskun, Ali
AU - Friedman, Douglas C.
AU - Forgan, Ross S.
AU - Sarjeant, Amy A.
AU - Trabolsi, Ali
AU - Fahrenbach, Albert C.
AU - Barin, Gokhan
AU - Paxton, Walter F.
AU - Dey, Sanjeev K.
AU - Olson, Mark A.
AU - Benítez, Diego
AU - Tkatchouk, Ekaterina
AU - Colvin, Michael T.
AU - Carmielli, Raanan
AU - Caldwell, Stuart T.
AU - Rosair, Georgina M.
AU - Hewage, Shanika Gunatilaka
AU - Duclairoir, Florence
AU - Seymour, Jennifer L.
AU - Slawin, A. M Z
AU - Goddard, William A.
AU - Wasielewski, Michael R.
AU - Cooke, Graeme
AU - Stoddart, J. Fraser
PY - 2010/10
Y1 - 2010/10
N2 - 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 over-ridden by stabilizing mixed-valence (TTF)2•+ and radical-cation (TTF •+)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. © 2010 Macmillan Publishers Limited. All rights reserved.
AB - 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 over-ridden by stabilizing mixed-valence (TTF)2•+ and radical-cation (TTF •+)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. © 2010 Macmillan Publishers Limited. All rights reserved.
UR - http://www.scopus.com/inward/record.url?scp=77957263792&partnerID=8YFLogxK
U2 - 10.1038/nchem.749
DO - 10.1038/nchem.749
M3 - Article
SN - 1755-4330
VL - 2
SP - 870
EP - 879
JO - Nature Chemistry
JF - Nature Chemistry
IS - 10
ER -