L. Wu et al.
ties were filtered out. The residual solution was extracted with chloro-
form (3ꢁ50 mL), and the combined chloroform solution was then dried
and evaporated under reduced pressure to dryness to give a yellow
liquid. The crude product was purified by using silica-gel column chroma-
tography (eluent: chloroform) to give a light-yellow liquid (yield: 1.7 g,
(0.09 g) under stirring, and its initial molar ratio to POM-1 was controlled
at 3.8:1. The organic phase was separated, washed with water (3ꢁ30 mL)
and dried over anhydrous sodium sulfate. SEP-D4 was obtained by evap-
orating the chloroform to dryness. The product was stored in a vacuum
desiccator until the weight remained constant (yield: 0.14 g, 82.4%).
1H NMR (CDCl3, TMS): d=0.85 (t, J=6.5 Hz, 12H; -CH3), 1.25–1.40
(m, 32H; -(CH2)4-CH3), 1.68–1.73 (m, 8H; -CH2-CH2-O-Ar), 3.16 (s, 9H;
(CH3)3N), 3.89 (t, J=6 Hz, 8H; -CH2-O-Ar), 4.39 (s, 2H; -CH2-NACHTUNGTRENNUNG(CH3)3),
4.92 (s, 4H; Ar-CH2-O-Ar), 6.34 (s, 2H; ArH para to -CH2OAr at the 4-
position), 6.56 (s, 4H; ArH ortho to -CH2OAr at the 2,6-positions), 6.62
1
92.1%). H NMR (CDCl3, TMS): d=0.89 (t, J=6.5 Hz, 6H; -CH3), 1.30–
1.34 (m, 12H; -(CH2)3-), 1.42–1.45 (m, 4H; -CH2-CH3), 1.75–1.77 (m,
4H; -CH2-CH2-O-Ar), 3.93 (t, J=6 Hz, 4H; -CH2-O-Ar), 4.62 (s, 2H;
-CH2-OH), 6.37 (s, 1H; ArH para to -CH2OH at the 4-position),
6.50 ppm (s, 2H; ArH ortho to -CH2OH at the 2,6-positions).
(s, 1H; ArH para to -CH2N
ACHTUGNERTN(NUNG CH3)3 at the 4-position), 6.69 ppm (s, 2H;
3,5-Bis(heptyloxy)benzyl bromide (4): Compound 3 (1.5 g, 4.4 mmol) was
dissolved in dry benzene (50 mL) and was cooled to 0–58C in an ice-
water bath. PBr3 (0.2 mL, 2.1 mmol) was added dropwise with stirring.
The mixture was stirred for another 6 h at room temperature, and doubly
distilled water (30 mL) was added to quench the reaction. The benzene
in the reaction solution was evaporated under vacuum, and the mixture
was extracted with dichloromethane (3ꢁ30 mL). The combined extracts
were dried with anhydrous sodium sulfate and evaporated to dryness.
The crude product was purified by using silica-gel column chromatogra-
phy (eluent: 1:1 (v/v) dichloroform/cyclohexane) to give a light-yellow
thick liquid product (yield: 1.7 g, 95.5%). 1H NMR (CDCl3, TMS): d=
0.89 (t, 6H; -CH3), 1.30–1.34 (m, 12H; -(CH2)3-), 1.42–1.45 (m, 4H;
-CH2-CH3), 1.75–1.77 (m, 4H; -CH2-CH2-O-Ar), 3.92 (t, 4H; -CH2-O-
Ar), 4.41 (s, 2H; -CH2-Br), 6.37 (s, 1H; ArH para to -CH2Br at the 4-po-
sition), 6.51 ppm (s, 2H; ArH ortho to CH2Br at the 2,6-positions).
ArH ortho to -CH2N(CH3)3 at the 2,6-positions); IR (KBr): n˜ =3435,
AHCTUNGTRENNUNG
2954, 2929, 2856, 1597, 1484, 1456, 1377, 1167, 1059, 972, 924, 885,
800 cmꢀ1; elemental analysis (%) calcd for SEP-D4 (C208H336N4O64W12Si,
6151.05): C 40.61, H 5.51, N 0.91; found: C 41.30, H 5.59, N 0.92 (corre-
sponding to the chemical formula: D4SiW12O40 (6151.05)); the TG mea-
surement displays a 53.3% (w/w) mass loss between 40 and 6008C.
SEP-D5: The complex was prepared by following a similar procedure as
for SEP-D4, but by using POM-2 instead of POM-1. The initial molar
ratio of dendritic molecule D to POM-2 was kept at 4.5:1 (yield: 0.03 g,
76.9%). 1H NMR (CDCl3, TMS): d=0.86 (t, J=6.5 Hz, 12H; -CH3),
1.26–1.39 (m, 32H; -(CH2)4-CH3), 1.70 (s, 8H; -CH2-CH2-O-Ar), 3.17 (s,
9H; (CH3)3N), 3.89 (s, 8H; -CH2-O-Ar), 4.45 (s, 2H; -CH2-NACHTUNGTRENNUNG(CH3)3),
4.93 (s, 4H; Ar-CH2-O-Ar), 6.35 (s, 2H; ArH para to -CH2OAr at the 4-
position), 6.56 (s, 4H; ArH ortho to -CH2OAr at the 2,6-positions), 6.61
(s, 1H; ArH para to -CH2N
ACHTUGNERTN(NUNG CH3)3 at the 4-position), 6.77 ppm (s, 2H;
3ꢀ,5ꢀ-BisACHTUNGTRENNUNG(3,5-bis(heptyloxy)benzyloxy)benzyl alcohol (5): Compound 4
ArH ortho to -CH2N(CH3)3 at the 2,6-positions); IR (KBr): n˜ =3440,
AHCTUNGTRENNUNG
(1.7 g, 4.3 mmol), 3,5-dihydroxybenzyl alcohol (0.25 g, 1.8 mmol), anhy-
drous K2CO3 (1.0 g, 7.2 mmol), and catalytic amount of 18-crown-6 were
dissolved in acetone (50 mL) and the mixture was stirred under reflux in
a N2 atmosphere for 24 h. The reaction was monitored by TLC analysis.
The reaction mixture was filtered and the excess solvent was evaporated.
The liquid mixture was then purified by using silica-gel column chroma-
tography (eluent: 10:1 (v/v) cyclohexane/ethyl acetate) to give a light-
yellow thick liquid (yield: 1.0 g, 72.1%). 1H NMR ([D6]DMSO, TMS):
d=0.86 (t, J=6.5 Hz, 12H; -CH3), 1.24–1.41 (m, 32H; -(CH2)4-CH3),
1.65–1.70 (m, 8H; -CH2-CH2-O-Ar), 3.92 (t, 8H; J=6.5 Hz, -CH2-O-Ar),
4.41 (d, J=6 Hz, 2H; -CH2-OH), 4.97 (s, 4H; Ar-CH2-O-Ar), 5.18 (t, J=
6 Hz, 1H; -OH), 6.39 (t, J=2 Hz, 2H; ArH para to -CH2OAr at the 4-
position), 6.49 (t, 1H; ArH para to -CH2OH at the 4-position), 6.54–
6.55 ppm (m, 4H and 2H; ArH ortho to -CH2OAr at the 2,6-positions
and ArH ortho to -CH2OH at the 2,6-positions).
2954, 2929, 2856, 1599, 1483, 1456, 1379, 1165, 1059, 993, 951, 903,
829 cmꢀ1; elemental analysis (%) calcd for SEP-D5 (C260H420N5O70W12B,
6953.00): C 44.91, H 6.09, N 1.01; found: C 45.72, H 5.85, N 0.64 (corre-
sponding to the chemical formula: D5BW12O40 (6953.00)); the TG mea-
surement displays a 60.8% (w/w) mass loss between 45 and 6008C.
SEP-D7: The complex was prepared by following a similar procedure as
for SEP-D4, but by using POM-3 instead of POM-1. The initial molar
ratio of dendritic molecule D to POM-3 was controlled at 6.5:1 (yield:
0.10 g, 78.1%). 1H NMR (CDCl3, TMS): d=0.85 (t, J=6.5 Hz, 12H;
-CH3), 1.25–1.36 (m, 32H; -(CH2)4-CH3), 1.68 (s, 8H; -CH2-CH2-O-Ar),
3.14 (s, 9H; (CH3)3N), 3.84 (s, 8H; -CH2-O-Ar), 4.49 (s, 2H; -CH2-N-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
3ꢀ,5ꢀ-BisACHTUNGTRENNUNG(3,5-bis(heptyloxy)benzyloxy)benzyl bromide (6): This compound
AHCTUNGTRENNUNG
was prepared from compound 5 by using a reaction procedure similar to
the preparation of compound 4. The crude product was directly used in
the following step without purification.
;
(C364H588N7O81W11SiNa or C364H588N7O81W11SiK, 8431.88 or 8447.99): C
51.85 or 51.75, H 7.03 or 7.02, N 1.16 or 1.16; found: C 51.52, H 7.00, N
0.58 (corresponding to the chemical formula: D7Na
or D7K(SiW11O39) (8447.99)); the TG measurement displays a 69.4% (w/
w) mass loss between 45 and 6008C.
N-3ꢀ,5ꢀ-bisACHTUNGTRENNUNG(3,5-bis(heptyloxy)benzyloxy)benzyl-N,N,N-trimethylammoni-
ACHTNUGNERT(NUGN SiW11O39) (8431.88)
um bromide (D): An aqueous solution of trimethylamine (33%, 0.7 g,
3.9 mmol) and crude product 6 (0.5 g) were dissolved in ethanol (50 mL),
and the mixture was stirred under reflux for 24 h with monitoring by
TLC analysis. The excess solvent and most of trimethylamine were
evaporated under vacuum. The thick liquid mixture was then purified by
using silica-gel column chromatography (eluent: 20:1 (v/v) chloroform/
methanol) to give a ceraceous solid (yield: 0.4 g, 69.1% over two steps).
1H NMR (CDCl3, TMS): d=0.89 (t, J=6.5 Hz, 12H; -CH3), 1.28–1.46
(m, 32H; -(CH2)4-CH3), 1.73–1.79 (m, 8H; -CH2-CH2-O-Ar), 3.32 (s, 9H;
(CH3)3N), 3.94 (t, J=6.5 Hz, 8H; -CH2-O-Ar), 4.89 (s, 2H; -CH2-N-
AHCTUNGTRENNUNG
SEP-D10: The complex was prepared by following a similar procedure as
for SEP-D4, but by using POM-4 instead of POM-1. The initial molar
ratio of dendritic molecule D to POM-4 was controlled at 8:1 (yield:
0.08 g, 88.9%). 1H NMR (CDCl3, TMS): d=0.86 (t, J=6.5 Hz, 12H;
-CH3), 1.26–1.38 (m, 32H; -(CH2)4-CH3), 1.70 (s, 8H; -CH2-CH2-O-Ar),
3.22 (s, 9H; (CH3)3N), 3.87 (s, 8H; -CH2-O-Ar), 4.49 (s, 2H; -CH2-N-
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
-CH2OAr at the 2,6-positions), 6.71 (t, 1H; ArH para to -CH2N
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
the 4-position), 6.83 ppm (d, J=2 Hz, 2H; ArH ortho to -CH2NAHCTUNGTRENNUNG
(KBr): n˜ =3435, 2954, 2927, 2856, 1599, 1484, 1456, 1379, 1167, 1122,
1080, 1059, 972, 937, 889, 816, 758 cmꢀ1; elemental analysis (%) calcd for
SEP-D10 (C520H840N10O116W15P2Na2, 11953.76): C 52.25, H 7.08, N 1.17;
found: C 52.00, H 6.37, N 1.00 (corresponding to the chemical formula:
D10Na2P2W15O56 (11953.76)); the TG measurement displays a 69.8% (w/
w) mass loss between 45 and 9008C.
the 2,6-positions); MALDI-TOF MS: m/z: 819.4 [M+]; IR (KBr): n˜ =
3423, 2954, 2929, 2856, 1597, 1488, 1462, 1379, 1167, 1059 cmꢀ1
.
Preparation of SEPs: All SEP complexes were prepared at room temper-
ature according to the previously reported procedures,[17] and were con-
firmed by 1H NMR and IR spectroscopy, elemental analysis, and TG
measurements.
Sample preparation for measurements: For the identification of the self-
assembled structures of dendritic molecule D and SEPs from acetone so-
lution, all of the sample films for XRD measurement were prepared
SEP-D4:
A solution of dendritic molecule D (0.1 g) in chloroform
(50 mL) was added dropwise into an aqueous solution (50 mL) of POM-1
8070
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 8062 – 8071