Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is © the Partner Organisations 2015
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A thermally stable pH-responsive “supramolecular buckle” based on the encapsulation of 4-(4-aminophenyl)-N-methylpyridinium by cucurbit[8]uril l
Tian-You Zhou, Qiao-Yan Qi, Ying Zhang, Xiao-Na Xu, and Xin Zhao* Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China Email:
[email protected] Contents
Figure S1 UV-vis spectra of 1 upon the addition of CB[8] and Job’s plot at pH = 7 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S2 Figure S2 ITC data for the titration of CB[8] with 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S2 Figure S3 UV-vis spectra of 1 upon the addition of CB[8] and Job’s plot at pH=1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S3 Figure S4 Variable-temperature 1H NMR spectra of CB[8] 1·H+ ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S3 Figure S5 Partial 1H NMR spectra of 1·H+, 2,6-dihydroxynaphthalene, and their mixture with CB[8] ∙∙∙S4 Figure S6 2D 1H NMR COSY spectrum of 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4 Figure S7 2D 1H NMR COSY spectrum of 1CB[8] (2:1)∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙ ∙∙∙∙∙∙∙S5 Figure S8 2D 1H NMR COSY spectrum of 1CB[8] (1:0.3)∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S6 Figures S9-10 1H NMR and 13C NMR spectra of 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S7
S1
0.4 0.08 1 1 + CB[8]
0.3
0.07 0.06 0.05
0.2
375 nm
Abs
Abs
368 nm
0.1
0.04 0.03 0.02
0.0 200
0.01
250
300
350
400
450
500
550
600
0.00 0.0
Wavelength (nm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
[1]/([1]+[CB[8]])
Figure S1. UV-vis spectra of 1 (13.3 μM) without and with CB[8] (6.7 μM) in water (pH = 7) at 25 oC (left), and Job’s plot indicating a 1:2 stoichiometery for CB[8] and 1 (right). The total concentration used for generating the Job’s plot was 20 μM.
Time (min) 0.20
-10 0
10 20 30 40 50 60 70 80 90 100 110
0.00 -0.20 -0.40
µcal/sec
-0.60 -0.80
Data: Data1_NDH Model: Sequential Binding Sites Chi^2/DoF = 3.711E4 -1 K1 2.20E4 ±1.7E3 M H1 4241 ±2.55E3 cal/mol S1 34.1 cal/mol/deg -1 K2 1.88E7 ±9.1E5 M H2 -1.915E4 ±2.57E3 cal/mol S2 -31.0 cal/mol/deg
-1.00 -1.20 -1.40 -1.60 -1.80 1.00
-1
kcal mol of injectant
0.00 -1.00 -2.00 -3.00 -4.00 -5.00 -6.00 -7.00 -8.00 -9.00 0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Molar Ratio
Figure S2. ITC data for the titration of CB[8] (0.1 mM) with 1 (2.0 mM) in a Tris-buffer solution (10 mM， pH 7.0) at 25 oC. S2
0.25 0.20 1. H
Abs
0.15
Abs
+
+
1.H + CB[8] 279 nm
0.10 0.05
368 nm 393 nm
0.00 200
250
300
350
400
450
500
550
600
0.022 0.020 0.018 0.016 0.014 0.012 0.010 0.008 0.006 0.004 0.002 0.000 -0.002
pH=1
0.0
0.1
Wavelength (nm)
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
[1]/([1]+[CB[8]])
Figure S3. UV-vis spectra of 1 (13.3 μM) without and with CB[8] (6.7 μM) in an aqueous hydrochloric acid solution (pH = 1.0) at 25 oC (left), and Job’s plot indicating a 1:1 stoichiometery for 1·H+ and CB[8] (right). The total concentration used for generating the Job’s plot was 20 μM.
Figure S4. Partial 1H NMR spectra (500 MHz) of CB[8]1·H+ at (a) 25 oC, (b) 40 oC, (c) 60 oC and (d) 75 o
C, and (e) 1·H+ at 75 oC in D2O. The spectra were calibrated by the temperature dependence of HDO
chemical shifts reported by H. E. Gottlieb et al. (J. Org. Chem. 1997, 61, 7512-7515.).
S3
Figure S5. 1H NMR spectra (500 MHz) of (a) 1·H+, (b) 2,6-dihydroxynaphthalene, and (c) mixture of 1·H+, 2,6-dihydroxynaphthalene and CB[8] (1:1:1) in D2O at pD=1.
Figure S6. 2D 1H NMR COSY spectrum (400 MHz, 293 K) of 1 in D2O.
S4
Figure S7. 2D 1H NMR COSY spectrum (400 MHz, 293 K) of the solution of 1 and CB[8] (2:1) in D2O.
S5
Figure S8. 2D 1H NMR COSY spectrum (400 MHz, 293 K) of the solution of 1 and CB[8] (1:0.3) in D2O.
S6
Figure S9. 1H NMR spectrum (500 MHz, DMSO-d6) of compound 1.
Figure S10. 13C NMR spectrum (125 MHz, DMSO-d6) of compound 1. S7
