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The "empty" host intermediate likely contains solvent (here water), although we have not been able to test this experimentally. As emphasized by a reviewer, the energetic penalties for complete desolvation of the host interior are probably quite large, and it is more plausible that the intermediate host is solvent filled. Throughout the manuscript, "empty" refers to the absence of the described guests and not the absence of solvent; we are not able to comment at this time on the role of encapsulated solvent in the guest exchange process. A distinct role of solvent in the guest exchange dynamics of hydrogen-bonded capsules has been demonstrated in another host-guest system: ref 13.
-
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65
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31944436098
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note
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+. The difference in treatment does not affect the determination of ΔH‡ and ΔV‡.
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31944431748
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It is likely that some rearrangement of the exterior ion-paired guests occurs as the host aperture dilates for guest exchange, and this process may contribute to the negative entropy of activation observed for the self-exchange reactions. For systems in which the bimolecular reaction with the G2 guest is rate limiting, the conformational rearrangement of the G2 guest required for it to pass through the host aperture will also contribute to the negative activation entropy.
-
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69
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31944444937
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note
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+ due to the temperature limitations of the variable pressure NMR probe.
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70
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31944450486
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note
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A positive volume of activation would also be expected for the bond-rupture mechanism, in which one ligand partially dissociates to open up a large host portal for guest egress. The volumes of activation for this mechanism, however, should be independent of guest size.
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-
Wanat, A.1
Schneppensieper, T.2
Stochel, G.3
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Bill, E.5
Wieghardt, K.6
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77
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0037029935
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Schneppensieper, T.; Wanat, A.; Stochel, G.; van Eldik, R. Inorg. Chem. 2002, 41, 2565-2573.
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Inorg. Chem.
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Schneppensieper, T.1
Wanat, A.2
Stochel, G.3
Van Eldik, R.4
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78
-
-
31944441894
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-
note
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+ exchange, produces similar kinetic behavior (Supporting Information).
-
-
-
-
79
-
-
31944452407
-
-
note
-
12- host.
-
-
-
-
80
-
-
0037345983
-
-
Saalfrank, R. W.; Demleitner, B.; Glaser, H.; Maid, H.; Reihs, S.; Bauer, W.; Maluenga, M.; Hampel, F.; Teichert, M.; Krautscheid, H. Eur. J. Inorg. Chem. 2003, 822-829.
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(2003)
Eur. J. Inorg. Chem.
, pp. 822-829
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-
Saalfrank, R.W.1
Demleitner, B.2
Glaser, H.3
Maid, H.4
Reihs, S.5
Bauer, W.6
Maluenga, M.7
Hampel, F.8
Teichert, M.9
Krautscheid, H.10
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81
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17544386475
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Márquez, C.; Hudgins, R. R.; Nau, W. M. J. Am. Chem. Soc. 2004, 126, 5806-5816.
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(2004)
J. Am. Chem. Soc.
, vol.126
, pp. 5806-5816
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Márquez, C.1
Hudgins, R.R.2
Nau, W.M.3
-
82
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31944448063
-
-
note
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Other ion pairing effects can be envisioned. For example, alkali cations are often found ion paired to the negatively charged catecholate caps of ML3 complexes. Large ammonium (or phosphonium) cation concentrations might interfere with this interaction thereby impacting the host dynamics. Additionally, interaction of the ammonium cations with the catecholate cap may itself be a critical parameter to host dynamics.
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-
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83
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31944438706
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Leung, D. H.; Bergman, R. G.; Raymond, K. N. Unpublished results
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Leung, D. H.; Bergman, R. G.; Raymond, K. N. Unpublished results.
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-
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84
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31944442331
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Fiedler, D.; van Halbeek, H.; Bergman, R. G.; Raymond, K. N. Unpublished results
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Fiedler, D.; van Halbeek, H.; Bergman, R. G.; Raymond, K. N. Unpublished results.
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-
-
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85
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31944443411
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note
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+.
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-
-
-
87
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9744264956
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Zahl, A.; Igel, P.; Weller, M.; van Eldik, R. Rev. Sci. Instrum. 2004, 75, 3152-3157.
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Rev. Sci. Instrum.
, vol.75
, pp. 3152-3157
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Zahl, A.1
Igel, P.2
Weller, M.3
Van Eldik, R.4
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