Table of Figures. Figure 1 Pseudorotaxanes and rotaxane Figure 2 [2]rotaxane based on dibenzo-24-crown-8 and a ammonium salt...

Transcription

1 Table of Figures Pseudorotaxanes and rotaxanes I Figure 1 Pseudorotaxanes and rotaxane Figure 2 [2]rotaxane based on dibenzo-24-crown-8 and a ammonium salt... 6 [2]rotaxane based on dipyrido-24-crown-8 and a ammonium salt.. 7 Figure 4 A fullerence-containing [2]pseudorotaxane. 8 Figure 5 Proposed mechanism for the excited-state dynamics of photoinduced coconformation changing rotaxane. 9 Figure 6 Cyclodextrins and their guest.. 11 Figure 7 Some metal-complexed rotaxanes made by Sauvage s group. 13 Figure 8 A rotaxane which can be used to construct molecular-based electronically switchable tunnel junction devices.. 15 Figure 9 A pseudorotaxane containing a π-electron-deficient linear component and a π- electron-rich macrocycle. 16 Figure 10 A [3]pseudorotaxane containing two dibenzo-24-crown-8 macrocycles and one linear scaffold 17 Figure 11 Threading of a hetero-guest pair into the cavity of cucurbit[8]uril. 18 Figure 12 The equilibrium formation of [2]-, [3]- and [4]-pseudorotaxanes from a homotritopic guest molecule and a complementary macrocycle host. 21 Figure 13 An azo dye [2]rotaxane 22 Figure 14 The first Janus [2]rotaxane.. 23 Figure 15 A [2]pseudorotaxane made from a homotritopic guest molecule and a homotritopic host molecule. 24 x

2 Figure 16 A novel [3]rotaxane containing one linear component, a neutral tetraamide cyclophane, and a tetracationic cyclophane. 25 Figure 17 A Job plot for 2:1 complexation of H with G.. 26 Figure 18 A mole ratio plot for 1:1 complexation of H with G Figure 19 Scatchard plots for complexation involving a multifunctional guest G: (a) cooperative complexation, (b) statistical complexation, and (c) anticooperative complexation 29 Figure 20 Resonance structures of dimethyl paraquat showing the acidity of methyl hydrogens (column a) and α pyridinium hydrogens (column b) 34 Figure 21 Resonance structures of dibenzylammoinium showing the acidity of ammonium hydrogens.. 34 III [2]Pseudorotaxanes Based on the Dibenzo-24-Crown-8/Paraquat Recognition Motif Figure 1 Partial 1 H NMR spectra (400 MHz, CD 3 COCD 3, 298K) of (a) 2.00 mm 4-2PF 6, (b) 2.00 mm 4-2PF 6 and 2.00 mm 3, (c) 2.00 mm Figure 2 Job plot: the stoichiometry of the complex between 3 and 4-2PF 6 in CD 3 COCD 3 solution using data for H 2 55 Partial 1 H NMR spectra (400 MHz, acetone-d 6, 298K) of (a) mm 3, (b) mm 3 and mm 4-2PF 6, (c) mm 3 and 10.0 mm 4-2PF 6, (d) mm 3 and 20.0 mm 4-2PF 6, (e) mm 3 and 40.0 mm 4-2PF 6, and (f) mm 3 and 60.0 mm 4-2PF 6 showing the chemical shift of H 2 at different concentrations of 4-2PF Figure 4 Relationship between 1/ and 1/[4-2PF 6 ] 0 for the complexation between 1 and 2 in acetone-d 6, 22 C xi

3 Figure 5 Fast-atom bombardment mass spectrum of a solution of 3 and 4-2PF 6 (1:1 molar ratio).. 58 Figure 6 Two views of the solid-state structure of 3 4-2PF 6 3 as determined by X-ray crystallography (a and b), a partial view of 3 4-2PF 6 3 showing 8 N + O interactions at one side of the complex (c), cartoon representation of 3 4-2PF 6 3 (d), and cartoon representation of 3 1-2PF 6 3 (e).. 62 Figure 7 Two views of the solid-state structure of 4-2PF 6 as determined by X-ray crystallography. 64 Figure 8 1 H NMR spectra (400 MHz, CD 3 COCD 3, 22 C) of (a) 1.00 mm 3, (b) 1.00 mm 3 and 1.00 mm 8a-2PF 6, (c) 1.00 mm 8a-2PF Figure 9 Job plot: the stoichiometry of the complex between 3 and 8a-2PF 6 in CD 3 COCD 3 solution using data for H 2 67 Figure 10 Partial 1 H NMR spectra (400 MHz, acetone-d 6, 298K) of (a) 1.00 mm 3, (b) 1.00 mm 3 and 1.00 mm 8a-2PF 6, (c) 1.00 mm 3 and 6.00 mm 8a-2PF 6, (d) 1.00 mm 3 and 11.0 mm 8a-2PF 6, (e) 1.00 mm 3 and 30.0 mm 8a-2PF 6, and (f) 1.00 mm 3 and 60.0 mm 8a-2PF 6 showing the chemical shift of H 2 at different concentrations of 8a-2PF Figure 11 Relationship between 1/ and 1/[8a-2PF 6 ] Figure 12 1 H NMR spectra (400 MHz, CD 3 COCD 3, 22 C) of (a) 1.00 mm 8b-2PF 6, (b) 1.00 mm 3 and 1.00 mm 8b-2PF 6, (c) 1.00 mm Figure 13 Job plot: the stoichiometry of the complex between 3 and 8b-2PF 6 in CD 3 COCD 3 solution using data for H Figure 14 Partial 1 H NMR spectra (400 MHz, acetone-d 6, 298K) of (a) 1.00 mm 3, (b) 1.00 mm 3 and 1.00 mm 8b-2PF 6, (c) 1.00 mm 3 and 5.00 mm 8b-2PF 6, (d) 1.00 mm 3 and 10.0 mm 8b-2PF 6, (e) 1.00 mm 3 and 20.0 mm 8b-2PF 6, (f) xii

4 1.00 mm 3 and 60.0 mm 8b-2PF 6, and (g) 1.00 mm 3 and mm 8b-2PF 6 showing the chemical shift of H 2 at different concentrations of 8b- 2PF Figure 15 Relationship between 1/ and 1/[8b-2PF 6 ] 0 for the complexation between 3 and 8b-2PF 6 in acetone-d 6, 22 C Figure 16 Relationship between 1/ and 1/[8c-2PF 6 ] 0 for the complexation between 3 and 8c-2PF 6 in acetone-d 6, 22 C. 75 Figure 17 Relationship between 1/ and 1/[8d-2PF 6 ] 0 for the complexation between 3 and 8d-2PF 6 in acetone-d 6, 22 C Figure 18 Relationship between 1/ and 1/[8e-2PF 6 ] 0 for the complexation between 3 and 8e-2PF 6 in acetone-d 6, 22 C. 77 IV Ion Pairing in Fast-Exchange Host-Guest Systems: Concentration Dependence of Apparent Association Constants for Complexes of Neutral Hosts and Divalent Guest Salts with Monovalent Counterions Figure 1 Mole ratio plot for 1 and 2, 22 C. The solvent is acetone-d 6. [1] 0 and [2] 0 are initial concentrations of 1 and 2. [1] 0 = 3.75 mm 97 Figure 2 Partial 1 H NMR spectra (400 MHz, acetone-d 6, 22 C) of (a) mm 1, (b) mm 1 and mm 2, (c) mm 1 and mm 2, (d) mm 1 and 1.50 mm 2, (e) mm 1 and 10.0 mm 2, (f) mm 1 and 15.0 mm 2, (g) mm 1 and 20.0 mm 2, and (h) mm 1 and 30.0 mm 2 showing the chemical shift of H 1 at different concentrations of 2 98 Relationship between 1/ and 1/[2] 0 for the complexation between 1 and 2 in acetone-d 6, 22 C.. 99 xiii

5 Figure 4 Log-log plot of Eq. 1d for the complexation between 1 and 2 in acetone-d 6, 22 C. 101 Figure 5 Relationship between K a,exp and 1/[1] uc 2/3 according to Eq. 1h for [2] uc < mm for the complexation between 1 and 2 in acetone-d 6, 22 C. Figure 6 Relationship between [1] uc 1/3 /[1] c and 1/[2] uc 2/3 according to Eq. 1i 103 Figure 7 X-ray crystal structure of the complex Figure 8 Cartoon representations of possible co-conformations of the 1:1 complex between 1 (blue) and 2 (red) in solution, showing the interactions between both benzo rings of 2 with both pyridinium rings of 1, thus preventing ion pairing of the complex. 105 Figure 9 Plot of Eq. 2b for the complexation between 1 and 4 in acetone-d 6, 22 C. 108 Figure 10 Plot of Eq. 2b for the complexation between 3 and 5 in acetone-d 6, 22 C. 109 Figure 11 X-ray crystal structures of (a) and (b) Figure 12 Plot of Eq. 2b for the complexation between 6 and 1 in acetone-d 6, C. Figure 13 Plot of Eq. 2b for the complexation between 6 and 7 in acetone-d 6, 22 C. 115 Figure 14 X-ray crystal structures of (a) and (b) Selectivity Studies Among Two Hosts and Two Guests V Figure 1 Compounds used in this study. 127 Figure 2 Partial 1 H NMR spectra (400 MHz, CD 3 COCD 3, 298K) of (a) 1.00 mm BPP34C10, (b) 1.00 mm DB24C8, (c) 1.00 mm 2, (d) 1.00 mm 1, (e) 1.00 xiv

6 mm BPP34C10 and 1.00 mm 1, (f) 1.00 mm DB24C8 and 1.00 mm 1, and (g) 1.00 mm DB24C8 and 1.00 mm Partial 1 H NMR spectra (400 MHz, CD 3 COCD 3, 298K) of (a) 1.00 mm BPP34C10, (b) 1.00 mm DB24C8 (c) 1.00 mm 1, (d) 1.00 mm BPP34C10, 1.00 mm DB24C8, and 1.00 mm Figure 4 Partial 1 H NMR spectra (400 MHz, CD 3 COCD 3, 298K) of (a) 1.00 mm DB24C8, (b) 1.00 mm 1 (c) 1.00 mm 2, (d) 1.00 mm DB24C8, 1.00 mm 1, and 1.00 mm VI A Star-Shaped Supramolecular Polymer: Cooperative Complexation between A Tetraparaquat Salt and A Dibenzo-24-Crown-8 Functionalized Polystyrene Oligomer Figure 1 Relationship between 1/ and 1/[2] 0 for the complexation between 1 and 2 in acetone-d 6, 22 C Figure 2 Mole ratio plot for 2 and 1. The solvent is acetone-d 6. [1] 0 = mm Scatchard plots for complexation of tetraparaquat guest 1 ([1] 0 = mm) with crown ether 2 in acetone-d 6 at 22 C Figure 4 Mole ratio plot for 3 and 1, indicating 3:1 stoichiometry Figure 5 Scatchard plots for complexation of tetraparaquat guest 1 ([1] 0 = mm) with polystyrl crown ether 3 in acetone-d 6 at 22 C xv