Synthesis, Characterization and Ion-Complexing Properties of
Polymers Displaying Densely Packed Arrays of Crown Ethers
as Lateral Substituents
Ming Liu, Sandrine Peyrat, Nicolas Illy, Véronique Wintgens, Blandine Brissault, Jacques
Penelle and Valessa Barbier*
†
Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris Est and CNRS, 2-8
rue Henri Dunant, 94320 Thiais, France
barbier@icmpe.cnrs.fr
* Corresponding author
- Table S1. Elemental analysis data of monomers and polymers
- Table S2. Glass transition temperature (Tg) of monomers measured by Differential Scanning Calorimetry (20°C/min).
- Table S3. Binding constants and thermodynamic parameters for complexation of Na+ and K+ with 1-6 and Poly1-Poly4 in
EtOH 95% at 298K.
- Figure S1. Poly1 (up) 1H NMR (400 MHz, (CD3)2CO, room temperature); (down)
13C
NMR (100 MHz, CDCl3, room
13C
NMR (100 MHz, CDCl3, room
13C
NMR (100 MHz, CDCl3, room
temperature)
- Figure S2. Poly2 (up) 1H NMR (400 MHz, (CD3)2CO, room temperature); (down)
temperature)
- Figure S3. Poly3 (up) 1H NMR (400 MHz, (CD3)2CO, room temperature); (down)
temperature)
- Figure S4. Thermogravimetric curve for Poly1 (a), Poly2 (b), Poly3 (c) and Poly4 (d) (10 K.min-1, under Ar).
- Figure S5. Integrated heat evolved per injection () after subtraction of the dilution heat for the titration of 1 (a), 3 (b), Poly1
(c) and Poly3 (d) by K+ solution. The lines represent the results of the best fit, whereas () shows the integrated heat released
per injection for K+ addition into ethanol.
- Figure S6. Picrate extraction experiments. Binding of cations (Li+, Na+ and K+) to monosubstituted monomers (),
disubstituted monomers (), monosubstituted polymers () and disubstituted polymers (): complexed cation concentration
over crown-ether [CE] initial concentration ratio as a function of cation (picrate) over CE initial concentration for (a,c) 15crown-5 systems; (b,d,e) 18-crown-6 systems. [CE] = 7 x 10-5 M.
Table S1. Elemental analysis data of monomers and polymers
Table S2. Glass transition temperature (Tg) of monomers measured by Differential Scanning Calorimetry (20°C/min).
Monomer
(1)
(2)
(3)
(4)
Tg (°C)
-67
-45
-58
-50
Table S3. Binding constants and thermodynamic parameters for complexation of Na+ and K+ with 1-6 and Poly1-Poly4
in EtOH 95% at 298K.
Ligand
1
2
3
4
5
6
Poly1
Poly2
Cation
Log(K)
- G°
- H°
TS°
N
Na+
3.15
17.97
24.51
-6.52
1.0*
K+
3.13
17.88
68.07
-50.12
0.5*
Na+
3.30
18.83
30.72
-11.86
0.5*
K+
5.28
30.12
71.13
-40.90
0.45
Na+
3.69
21.05
48.16
-27.12
0.47
K+
5.32
30.36
47.99
-17.58
0.65
Na+
3.34
19.07
90.17
-70.94
0.5*
K+
4.71
26.84
50.63
-23.81
0.62
Na+
3.50
19.94
30.46
-10.49
0.95
K+
3.47
19.80
71.96
-52.12
0.50
Na+
3.94
22.46
43.51
-21.32
0.35
K+
5.24
29.87
53.26
-23.32
0.52
Na+
2.95
16.85
51.17
-34.29
0.16
K+
3.97
22.65
121.42
-98.62
0.25
Na+
3.25
18.53
48.37
-29.80
0.14
K+
3.98
22.71
101.99
-79.17
0.35
4.40
25.08
44.18
-19.08
0.08
3.02
17.21
21.16
-3.93
0.90
5.38
30.68
45.44
-14.71
0.17
3.59
20.48
41.88
-21.32
1.01
4.57
26.08
75.06
-48.88
0.02
3.43
19.55
11.46
-8.10
1.02
5.50
31.39
39.47
-8.04
0.20
3.14
17.91
85.98
-67.95
0.66
Na+
Poly3
K+
Na+
Poly4
K+
*value of n, number of cations bound / ligand, was fixed
Figure S1. Poly1 (up) 1H NMR (400 MHz, (CD3)2CO, room temperature); (down) 13C NMR (100 MHz, CDCl3, room
temperature)
Figure S2. Poly2 (up) 1H NMR (400 MHz, (CD3)2CO, room temperature); (down) 13C NMR (100 MHz, CDCl3, room
temperature)
Figure S3. Poly3 (up) 1H NMR (400 MHz, (CD3)2CO, room temperature); (down) 13C NMR (100 MHz, CDCl3, room
temperature)
Figure S4. Thermogravimetric curve for Poly1 (a), Poly2 (b), Poly3 (c) and Poly4 (d) (10 K.min-1, Ar).
Figure S5. Integrated heat evolved per injection () after subtraction of the dilution heat for the titration of 1 (a), 3 (b), Poly1
(c) and Poly3 (d) by K+ solution. The lines represent the results of the best fit, whereas () shows the integrated heat released
per injection for K+ addition into ethanol.
Figure S6. Picrate extraction experiments. Binding of cations (Li+, Na+ and K+) to monosubstituted monomers (),
disubstituted monomers (), monosubstituted polymers () and disubstituted polymers (): complexed cation concentration
over crown-ether [CE] initial concentration ratio as a function of cation (picrate) over CE initial concentration for (a,c) 15crown-5 systems; (b,d,e) 18-crown-6 systems. [CE] = 7 x 10-5 M.