Abstract
Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis (paraquat-p- phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.
| Original language | English |
|---|---|
| Pages (from-to) | 429-433 |
| Number of pages | 5 |
| Journal | Science |
| Volume | 339 |
| Issue number | 6118 |
| DOIs | |
| Publication status | Published - Jan 25 2013 |
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A radically configurable six-state compound. / Barnes, Jonathan C.; Fahrenbach, Albert C.; Cao, Dennis; Dyar, Scott M.; Frasconi, Marco; Giesener, Marc A.; Benítez, Diego; Tkatchouk, Ekaterina; Chernyashevskyy, Oleksandr; Shin, Weon Ho; Li, Hao; Sampath, Srinivasan; Stern, Charlotte L.; Sarjeant, Amy A.; Hartlieb, Karel J.; Liu, Zhichang; Carmieli, Raanan; Botros, Youssry Y.; Choi, Jang Wook; Slawin, Alexandra M Z; Ketterson, John B.; Wasielewski, Michael R; Goddard, William A.; Stoddart, J. Fraser.
In: Science, Vol. 339, No. 6118, 25.01.2013, p. 429-433.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - A radically configurable six-state compound
AU - Barnes, Jonathan C.
AU - Fahrenbach, Albert C.
AU - Cao, Dennis
AU - Dyar, Scott M.
AU - Frasconi, Marco
AU - Giesener, Marc A.
AU - Benítez, Diego
AU - Tkatchouk, Ekaterina
AU - Chernyashevskyy, Oleksandr
AU - Shin, Weon Ho
AU - Li, Hao
AU - Sampath, Srinivasan
AU - Stern, Charlotte L.
AU - Sarjeant, Amy A.
AU - Hartlieb, Karel J.
AU - Liu, Zhichang
AU - Carmieli, Raanan
AU - Botros, Youssry Y.
AU - Choi, Jang Wook
AU - Slawin, Alexandra M Z
AU - Ketterson, John B.
AU - Wasielewski, Michael R
AU - Goddard, William A.
AU - Stoddart, J. Fraser
PY - 2013/1/25
Y1 - 2013/1/25
N2 - Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis (paraquat-p- phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.
AB - Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis (paraquat-p- phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.
UR - http://www.scopus.com/inward/record.url?scp=84872773951&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84872773951&partnerID=8YFLogxK
U2 - 10.1126/science.1228429
DO - 10.1126/science.1228429
M3 - Article
C2 - 23349286
AN - SCOPUS:84872773951
VL - 339
SP - 429
EP - 433
JO - Science
JF - Science
SN - 0036-8075
IS - 6118
ER -