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We use the nomenclature [2/3]pseudorotaxane to convey that the bistability of the supramolecular systems switches the structure between the [2]- and [3]pseudorotaxane forms and to contrast this with redox-driven complexes that disassemble into their component parts, for example, as seen in ref 37.
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The IUPAC uses both disproportionation and dismutation to identify the general class of reactions: A + A ⇁ A' + A", where A, A', and A" are different chemical species. The use of "dismutation" is used to distinguish the supramolecular reaction studied herein from the more common usage of disproportionation to describe changes in oxidation state.
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The effect of differences in ligand basicity on reaction rates will be considered as and when appropriate. The known basicity pKBH , in the neutral state has been reported;
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+) in the neutral state has been reported;
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The degree to which reduction enhances basicity is proportional to the ease of reduction and follows the order: E(red, 0.8 V (tetrazine) <-2.1 V (pyrazine, 2.1 V (pyridazine) <-2.7 V pyridine
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Coordinated 2,2′-bipyridine: Grummt, U. W.; Erhardt, S. J. Mol. Struc. Theochem. 2004, 685, 133-137.
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Coordinated 2,2′-bipyridine: Grummt, U. W.; Erhardt, S. J. Mol. Struc. Theochem. 2004, 685, 133-137.
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199
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76149119557
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2+.
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2+.
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202
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0002199350
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For calculations of the LUMO for bis-bidentate ligands see: a
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For calculations of the LUMO for bis-bidentate ligands see: (a) Kaim, W.; Kohlmann, S. Inorg. Chem. 1987, 26, 68-77.
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Kaim, W.1
Kohlmann, S.2
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203
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0000063804
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-
(b) Schwach, M.; Hausen, H. D.; Kaim, W. Inorg. Chem. 1999, 38, 2242-2243.
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Inorg. Chem
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Schwach, M.1
Hausen, H.D.2
Kaim, W.3
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204
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0036193479
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(bb) Gordon, K. C.; Burrell, A. K.; Simpson, T. J.; Page, S. E.; Kelso, G.; Polson, M. I. J.; Flood, A. Eur. J. Inorg. Chem. 2002, 554-563.
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(2002)
Eur. J. Inorg. Chem
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Gordon, K.C.1
Burrell, A.K.2
Simpson, T.J.3
Page, S.E.4
Kelso, G.5
Polson, M.I.J.6
Flood, A.7
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205
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33645695975
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(c) Remenyi, C.; Reviakine, R.; Kaupp, M. J. Phys. Chem. A 2006, 110, 4021-4033.
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(2006)
J. Phys. Chem. A
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Remenyi, C.1
Reviakine, R.2
Kaupp, M.3
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206
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69049109835
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(d) Li, G.; Parimal, K.; Vyas, S.; Hadad, C. M.; Flood, A. H.; Glusac, K. D. J. Am. Chem. Soc. 2009, 131, 11656-11657.
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(2009)
J. Am. Chem. Soc
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Li, G.1
Parimal, K.2
Vyas, S.3
Hadad, C.M.4
Flood, A.H.5
Glusac, K.D.6
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207
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76149122615
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65 and prefer transoid conformations.
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65 and prefer transoid conformations.
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208
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76149093966
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2+ · · · pyridine) interactions.
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2+ · · · pyridine) interactions.
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-
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209
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35948981559
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The observation of cation-π interactions involving Cu(I) suggests this pathway will also be available in the [2]pseudorotaxanes, see: (c) Ruan, C.; Yang, Z.; Rodgers, M. Phys. Chem. Chem. Phys. 2007, 9, 5902-5918.
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The observation of cation-π interactions involving Cu(I) suggests this pathway will also be available in the [2]pseudorotaxanes, see: (c) Ruan, C.; Yang, Z.; Rodgers, M. Phys. Chem. Chem. Phys. 2007, 9, 5902-5918.
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211
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76149096954
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66 Therefore, reduction should retain the flexibility of the neutral species.
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66 Therefore, reduction should retain the flexibility of the neutral species.
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212
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76149129819
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The products of the initial ligand exchange reactions may need to undergo bond rotations to access the stable forms of the reduced [3]pseudorotaxanes. These stable forms are expected to be syn for TZ and CF 3TZ, where stacking between phenanthrolines can occur. 52,56 For PZ and PD, their respective anti and syn orientations are predetermined by their central pyrazine and pyridazine heterocycles. For the initially formed [3]pseudorotaxane with a monodentate transoid-PZ, only the pyridyl heterocycle has to rotate. On the basis of the four-coordinate [Zn(H2O)22,2-bipyridine] 2+ model63 and the impact of reduction, a small-to-absent barrier can be expected. For the monodentate transoid-PD and bidentate anti-TZ, rotation of the larger {macrocycle-Cu-pyridyl, moiety is required, with possible benefits from a cation-π interaction.63,67c,d Las
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+ moiety is required, with possible benefits from a cation-π interaction.63,67c,d Lastly, for the possible monodentate syn-TZ product, multiple rotational pathways are possible.
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214
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0000430124
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(b) Evans, D. H. Chem. Rev. 1990, 90, 739-751.
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Evans, D.H.1
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215
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76149091314
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Rudolph, M.; Feldberg, S. W. DigiSim 3.03b; Bioanalytical Systems Inc.: West Lafayette, IN, accessed June 30, 2009.
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Rudolph, M.; Feldberg, S. W. DigiSim 3.03b; Bioanalytical Systems Inc.: West Lafayette, IN, accessed June 30, 2009.
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216
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38949158373
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Vander Griend, D. A.; Bediako, D. K.; DeVries, M. J.; DeJong, N. A.; Heeringa, L. P. Inorg. Chem. 2008, 47, 656-662.
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Vander Griend, D.A.1
Bediako, D.K.2
DeVries, M.J.3
DeJong, N.A.4
Heeringa, L.P.5
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217
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0000071215
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(a) Miller, S. R.; Gustowski, D. A.; Chen, Z. H.; Gokel, G. W.; Echegoyen, L.; Kaifer, A. E. Anal. Chem. 1988, 60, 2021-2024.
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Miller, S.R.1
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Chen, Z.H.3
Gokel, G.W.4
Echegoyen, L.5
Kaifer, A.E.6
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218
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33751156895
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(b) Cordova, E.; Bissell, R. A.; Kaifer, A. E. J. Org. Chem. 1995, 60, 1033-1038.
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0032536556
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(c) Boulas, P. L.; Gomez-Kaifer, M.; Echegoyen, L. Angew. Chem., Int. Ed. 1998, 37, 216-247.
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Boulas, P.L.1
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(d) Kim, H. J.; Jeon, W. S.; Ko, Y. H.; Kim, K. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 5007-5011.
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Kim, H.J.1
Jeon, W.S.2
Ko, Y.H.3
Kim, K.4
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221
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32644432897
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Maji, S.; Sarkar, B.; Patra, S.; Fielder, J.; Mobin, S. M.; Puranik, V. G.; Kaim, W.; Lahiri, G. K. Inorg. Chem. 2006, 45, 1316-1325.
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Maji, S.1
Sarkar, B.2
Patra, S.3
Fielder, J.4
Mobin, S.M.5
Puranik, V.G.6
Kaim, W.7
Lahiri, G.K.8
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222
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76149126232
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b units.
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b units.
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