Abstract
Supramolecular interactions of polynitroxides with γ-cyclodextrin (γ-CD) were used to control intramolecular electron spin-spin exchange couplings in these stable radicals. In the absence of γ-CD, the binitroxide T2 and trinitroxide T3 showed strong spin-spin coupling as evidenced by the high exchange coupling constant of J = 120 MHz for T2 in its EPR spectra. Host/guest complexes are formed upon addition of γ-CD to the polynitroxides where the nitroxide moiety interacts with the γ-CD cavity, which causes suppression of spin exchange. By variation of the host/guest ratio, the nature of a trinitroxide spin system can be tuned from a three-spin to a two-spin to a one-spin system. In addition to the host/guest ratio, the spin exchange coupling can also be tuned by temperature, which shifts the equilibrium between CD-encapsulated nitroxides and free nitroxides.
| Original language | English |
|---|---|
| Pages (from-to) | 427-431 |
| Number of pages | 5 |
| Journal | RSC Advances |
| Volume | 3 |
| Issue number | 2 |
| DOIs | |
| State | Published - Jan 14 2013 |
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ASJC Scopus subject areas
- Chemical Engineering(all)
- Chemistry(all)
Cite this
Control of spin-spin exchange interactions in polynitroxides through inclusion within γ-cyclodextrin. / Porel, Mintu; Ottaviani, M. Francesca; Jockusch, Steffen; Turro, Nicholas J.; Ramamurthy, Vaidhyanathan.
In: RSC Advances, Vol. 3, No. 2, 14.01.2013, p. 427-431.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Control of spin-spin exchange interactions in polynitroxides through inclusion within γ-cyclodextrin
AU - Porel, Mintu
AU - Ottaviani, M. Francesca
AU - Jockusch, Steffen
AU - Turro, Nicholas J.
AU - Ramamurthy, Vaidhyanathan
PY - 2013/1/14
Y1 - 2013/1/14
N2 - Supramolecular interactions of polynitroxides with γ-cyclodextrin (γ-CD) were used to control intramolecular electron spin-spin exchange couplings in these stable radicals. In the absence of γ-CD, the binitroxide T2 and trinitroxide T3 showed strong spin-spin coupling as evidenced by the high exchange coupling constant of J = 120 MHz for T2 in its EPR spectra. Host/guest complexes are formed upon addition of γ-CD to the polynitroxides where the nitroxide moiety interacts with the γ-CD cavity, which causes suppression of spin exchange. By variation of the host/guest ratio, the nature of a trinitroxide spin system can be tuned from a three-spin to a two-spin to a one-spin system. In addition to the host/guest ratio, the spin exchange coupling can also be tuned by temperature, which shifts the equilibrium between CD-encapsulated nitroxides and free nitroxides.
AB - Supramolecular interactions of polynitroxides with γ-cyclodextrin (γ-CD) were used to control intramolecular electron spin-spin exchange couplings in these stable radicals. In the absence of γ-CD, the binitroxide T2 and trinitroxide T3 showed strong spin-spin coupling as evidenced by the high exchange coupling constant of J = 120 MHz for T2 in its EPR spectra. Host/guest complexes are formed upon addition of γ-CD to the polynitroxides where the nitroxide moiety interacts with the γ-CD cavity, which causes suppression of spin exchange. By variation of the host/guest ratio, the nature of a trinitroxide spin system can be tuned from a three-spin to a two-spin to a one-spin system. In addition to the host/guest ratio, the spin exchange coupling can also be tuned by temperature, which shifts the equilibrium between CD-encapsulated nitroxides and free nitroxides.
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U2 - 10.1039/c2ra22285j
DO - 10.1039/c2ra22285j
M3 - Article
AN - SCOPUS:84870884918
VL - 3
SP - 427
EP - 431
JO - RSC Advances
JF - RSC Advances
SN - 2046-2069
IS - 2
ER -