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NP lee wa s eJ od uo r nn oa tl aod fj uC s ht em ma ri sg it nr ys
DOI: 10.1039/C7NJ03175K
Journal Name
ARTICLE
g/mol, 2 mmol, 0.53 g). After stirring for 36h, the reaction = 8.6, 7.2 Hz, 2H), 4.48 (t, J = 5.8 Hz, 1H), 4.41 (d, J = 1.1 Hz,
solution was allowed to cool down to room temperature. The 1H), 4.30-4.23 (m, 2H), 4.05 (d, J = 8.1 Hz, 1H), 3.79 (d, J = 8.5
deionized water (100 mL) was poured into the reaction and Hz, 1H), 3.69-3.64 (m, 1H), 3.63-3.57 (m, 3H), 3.47-3.41 (m,
1
3
the mixture stirred for another 2 h. The crude product was 1H), 2.07-1.94 (m, 2H). C NMR (101 MHz, DMSO-d ): δ
6
2 2
extracted with CH Cl and dried with magnesium sulfate. After 168.71 (s), 167.15 (s), 157.09 (s), 155.38 (s), 149.66 (s), 139.22
filtration and removing the solvent in vacuo, the crude product (s), 137.76 (s), 131.86 (s), 131.36 (s), 130.83 (s), 130.62 (s),
was purified by column chromatography (CH Cl :CH OH=50:1) 129.21 (s), 127.49 (s), 124.88 (s), 121.35 (s), 107.29 (s), 98.56
2
2
3
1
to give the white solid 5a (0.6337g, 89%). H NMR (400 MHz, (s), 80.76 (s), 79.76 (s), 69.51 (s), 66.52 (s), 62.95 (s), 35.80 (s),
+
CDCl
3
): δ 8.70 (d, J = 4.0 Hz, 1H), 8.68-8.60 (m, 1H), 8.03 (s, 29.33 (s). HRMS (ESI-Q-TOF): m/z calc. for C31
2 4 7
H31Cl N O (M+H)
1
6
H), 7.87 (td, J = 7.8, 1.7 Hz, 1H), 7.44-7.31 (m, 1H), 4.35 (t, J = : 641.1570, found: 641.1563.
1
3
.1 Hz, 1H), 2.98 (t, J = 6.8 Hz, 1H), 2.12-1.98 (m, 1H). C NMR Compound C6S. C6 terpyridine amine 5b (1.05 g, 3 mmol),
): δ 167.09 (s), 157.04 (s), 156.05 (s), 148.98 (0.73 g, 2 mmol) and DMAP (4-dimethylaminopyridine, 0.01 g),
s), 136.78 (s), 123.81 (s), 121.34 (s), 107.37 (s), 66.14 (s), dissolved in anhydrous methanol (20 mL) were heated to
8
(101 MHz, CDCl
3
(
3
8.97 (s), 32.41 (s). HRMS (ESI-Q-TOF): m/z calc. for C18
H
19
N
4
O
reflux for 36 h under mechanical stirring. After cooling to room
+
M+H) : 307.1559, found: 307.1557.
(
temperature, the solid was separated by filtration, washing
1
Compound 5b. KOH (0.56 g, 10 mmol) and 6-amino-1-hexanol with methanol to get the product C6S (0.96 g, 70%). H NMR
(117 g/mol, 2 mmol, 0.234 g) were mixed in anhydrous DMSO (500 MHz, DMSO-d ): δ 8.70 (d, J = 4.1 Hz, 2H), 8.60 (d, J = 7.9
6
(10 mL) in a round bottom flask (50 mL). The suspension was Hz, 2H), 8.00 (td, J = 7.8, 1.5 Hz, 2H), 7.95 (s, 2H), 7.87 (d, J =
heated to 65
addition of (268 g/mol, 2 mmol, 0.53 g). After stirring for 24 1H), 4.73 (dd, J = 10.4, 7.2 Hz, 2H), 4.47 (t, J = 5.8 Hz, 1H), 4.34
and stirred for 30 min, followed by the 1.5 Hz, 1H), 7.64 (d, J = 8.3 Hz, 1H), 7.55-7.47 (m, 4H), 5.65 (s,
4
h, the reaction solution was allowed to cool down to room (s, 1H), 4.22 (t, J = 6.3 Hz, 2H), 4.00 (d, J = 8.0 Hz, 1H), 3.74 (d, J
temperature. After deionized water (100 mL) was poured into = 8.6 Hz, 1H), 3.64 (s, 1H), 3.53 (d, J = 5.8 Hz, 1H), 3.18-3.10 (m,
the reaction, the mixture was stirred for another 6 h and 2H), 1.82-1.76 (m, 2H), 1.50-1.43 (m, 4H), 1.35 (d, J = 7.2 Hz,
1
3
allowed to precipitate overnight. After filtration and dryness, 2H). C NMR (126 MHz, DMSO-d
the solid (0.6779 g) was purified by column chromatography 162.10 (s), 160.33 (s), 154.72 (s), 154.55 (s), 144.22 (s), 142.71
CH Cl :CH OH=20:1) to give the white solid 5b (0.5725g, 83%). (s), 136.84 (s), 136.32 (s), 135.63 (s), 134.18 (d, J = 14.8 Hz),
6
): δ 173.30 (s), 172.17 (s),
(
2
2
3
1
H NMR (400 MHz, CDCl
t, J = 6.6 Hz, 1H), 8.04-7.97 (m, 1H), 7.86 (ddd, J = 9.5, 6.3, 2.4 14.0 Hz), 103.50 (s), 85.69 (s), 84.73 (s), 74.47 (s), 73.38 (s),
Hz, 1H), 7.40-7.29 (m, 1H), 4.23 (t, J = 6.3 Hz, 1H), 2.87 (t, J = 67.86 (d, J = 13.9 Hz), 43.69 (s), 34.60 (s), 33.79 (s), 31.49 (s),
3
): δ 8.70 (dd, J = 2.8, 1.9 Hz, 1H), 8.62 132.49 (s), 129.88 (s), 126.30 (d, J = 18.2 Hz), 112.17 (d, J =
(
7
1
1
2 4 7
.3 Hz, 1H), 1.87 (dd, J = 14.1, 6.5 Hz, 1H), 1.73-1.60 (m, 1H), 30.56 (s). HRMS (ESI-Q-TOF): m/z calc. for C34H37Cl N O
1
.60-1.45 (m, 2H). C NMR (126 MHz, CDCl
3
+
3
): δ 167.50 (s), (M+H) : 683.2039, found: 683.2051.
57.24 (s), 156.38 (s), 149.20 (s), 136.96 (s), 123.97 (s), 121.54 Gel property
(
s), 107.60 (s), 68.30 (s), 42.29 (s), 33.79 (s), 29.20 (s), 26.79 (s),
+
Heating and cooling method: 20 mg C3S/C6S and 1 mL solvent
2
6.06 (s). HRMS (ESI-Q-TOF): m/z calc. for C21
49.2082, found: 349.2085.
25 4
H N O (M+H) :
mixed in the test tube (φ=10 mm) were heated until the
gelators were dissolved or could not be dissolved ever. Then
the solution was cooled to room temperature, staying
overnight. Water dilution method: 4 mg gelator and 0.5 mL
organic solvent were mixed into the test tube (φ=10 mm) until
the solid was fully dissolved, and then 0.5 mL deionized water
was added. After 1 min, if the system results in the solid-liquid
stratification, it is judged as precipitation (P). If the compound
is completely dissolved and transparent solution is obtained, it
is judged as dissolved (S). If the system has no liquid flowing
after inverting, it is judged as gel (G); If the system has little
liquid flowing after inverting, it is judging as weak gel (WG).
3
Compound 8. 50% D-gluconic acid
6 (215.8 g, 0.55 mol)
aqueous solution, concentrated hydrochloric acid (200 mL) and
methanol (100 mL) were mixed into a 2 L flask. After vigorous
stirring for 30 min, a solution of
7 (87.5 g, 0.5 mol) in methanol
(300 mL) was added with stirring continued. Then 100 mL
deionized water was added after 20 h. After stirring for
another 2 h, the solid was separated by filtration, washed with
deionized water and hot methylene chloride to get the
product
Compound C3S. C3 terpyridine amine 5a (1.84 g, 6 mmol), 8
0.73 g, 2 mmol) and DMAP (4-dimethylaminopyridine, 0.01 g),
8 (140 g, 76%).
(
Rare earth ions permeation: The solution of Eu(NO
3 3 2
·
) 6H O,
dissolved in anhydrous methanol (20 mL) were heated to
reflux for 36h under mechanical stirring. After cooling to room
temperature, the solid was separated by filtration, washed
Eu(CF SO ) or Tb(NO ) 6H O in acetonitrile with the
·
3
3
3
3
3
2
concentrate of 0.2 M was coated on the surface of the gel
prepared. The rare earth ions were penetrated into the gel
network which was monitored by ultraviolet lamp, and then
the surface of gel was washed with acetonitrile several times.
1
with methanol to get the product C3S (0.87 g, 68%). H NMR
(400 MHz, DMSO-d
6
): δ 8.70 (dd, J = 4.7, 0.7 Hz, 2H), 8.60 (d, J
=
7
1
7.9 Hz, 2H), 8.03-7.93 (m, 4H), 7.88 (d, J = 1.8 Hz, 1H), 7.76-
T
gel was measured by ball-drop method. A small glass ball (d =
.36 cm, m = 0.18 g) was placed on the surface of the gel in the
.68 (m, 1H), 7.61 (d, J = 8.3 Hz, 1H), 7.55 (dd, J = 8.4, 1.8 Hz,
H), 7.48 (ddd, J = 7.4, 4.8, 1.0 Hz, 2H), 5.69 (s, 1H), 4.77 (dd, J
0
test tube. After sealing and placing the test tube in the oil bath
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