Formation of Nanoarchitectures Including Pd Clusters
A R T I C L E S
Experimental Section
(10 mL) was added at the same temperature, and the mixture was stirred
for 24 h at room temperature. After the mixture was cooled to 0 °C
and diluted with diethyl ether, saturated aqueous ammonium chloride
was added to quench the reaction, and the aqueous layer was then
extracted with diethyl ether. The combined organic layers were dried
over sodium sulfate, and the solvent was removed under reduced
pressure. The residue was purified by silica gel column chromatography
General. H and 13C NMR spectra were recorded on a JEOL JNM-
1
LA300, JNM-LA400 spectrometer in CDCl
Tetramethylsilane was used as an internal standard (δ ) 0) for H NMR,
and the CDCl solvent peak was used as the internal standard (δ )
7.0) for C NMR. 2-Phenylpropene, N-bromosuccineimide (NBS),
3
unless otherwise noted.
1
3
1
3
7
bromobenzene, glycidol, styrene, tetraethyleneglycol, R-naphthyliso-
cyanate, quinoline, iodobenzene, and 4-(dimethylamino)pyridine were
purchased from Tokyo Chemical Industry. 1-[3-(Dimethylamino)-
propyl]-3-ethylcarbodiimide hydrochloride (EDCI) was purchased from
Aldrich. AIBN, ethyl acrylate, potassium carbonate, 4-iodobenzoic acid,
and t-AmOH were purchased from Wako Pure Chemical Industry.
Merrifield resin HL (1% DVB, 100-200 mesh) and N-methylami-
nomethyl polystyrene resin (8, 1% DVB, 100-200 mesh) were
purchased from Novabiochem. ArgoPore Wang Resin was purchased
from Argonaut. The glass used as a support was purchased from
(
hexane/EtOAc) to afford 2-[(2-phenylallyloxy)methyl]oxirane (2.66
1
g, 70%). H NMR (CDCl
3
) δ ) 2.59 (dd, 1H, J ) 2.7, 5.1 Hz), 2.78
(dd, 1H, J ) 4.2, 5.1 Hz), 3.13-3.17 (m, 1H), 3.46 (dd, 1H, J ) 5.8,
1
1
5
5
3
1
1.5 Hz), 3.77 (dd, 1H, J ) 3.2, 11.5 Hz), 4.41 (ddd, 1H, J ) 0.7, 1.2,
2.9 Hz), 4.48 (ddd, 1H, J ) 0.5, 1.2, 12.9 Hz), 5.34-5.36 (m, 1H),
13
.53-5.54 (m, 1H), 7.45-7.48 (m, 5H); C NMR (CDCl
3
) δ ) 44.3,
0.8, 70.5, 73.2, 114.6, 126.0, 127.8, 128.4, 138.6, 143.9; IR (KBr)
000, 2924, 2867, 1911, 1812, 1701, 1630, 1512, 1479, 1407, 1337,
-1
254, 1205, 1107, 991, 909, 839 cm ; HRMS (EI): Calcd for C13
H O
16 2
+
(M ), 190.0994; found, 190.0998.
3 4
MATSUNAMI Glass. Pd(PPh ) and trifluoroacetic acid were purchased
Preparation of Copolymer (2). Styrene (7.53 g, 72.3 mmol), 2-[(2-
from Kanto Chemical. Dry solvents (THF, DCM, DMF) were purchased
from Wako Pure Chemical Industry. Tetraethyleneglycol mono-2-
phenyl-2-propenyl ether was prepared according to the literature.10
Column chromatography was performed on silica gel 60 (Merck), and
preparative TLC was carried out by using Wakogel B-5F (Wako Pure
Chemical Industry). XRF analysis was performed by Shimadzu EDX-
phenylallyloxy)methyl]oxirane (1.72 g, 9.04 mmol), tetraethyleneglycol
mono-2-phenyl-2-propenyl ether (2.81 g, 9.04 mmol), and AIBN (105.9
mg, 0.65 mmol) were mixed in chloroform (11.5 mL). The mixture
was stirred for 48 h at reflux and then cooled to room temperature.
The resulting polymer solution was poured slowly into methanol. The
precipitated polymer was filtered and washed with methanol several
times and dried for 24 h under reduced pressure to afford the desired
8
00.
Microscopic Analysis. TEM images were obtained using a JEOL
copolymer (2, 7.35 g, 61% yield). The molar ratio of the components
JEM-1200EX II instrument operated at 80 kV. TEM specimens of all,
except for 6b, were prepared by placing a drop of the solution on
carbon-coated Cu grids and allowed to dry in air (without staining).
For the TEM specimen of 6b, a drop of the suspension of 6b in MeOH,
which was ground in a mortar with a pestle after freeze-drying with
benzene, was placed on a Cu grid. SEM images were obtained using
a Topcon LS-750 instrument operated at 10 kV. SEM specimens of all
were coated with platinum for 60 s in a sputter coater (Polaron SC
1
was determined by H NMR analysis (x/y/z ) 91:5:4). M
w
: 31 912,
M
n
: 19 468, M
Preparation of Pd-Containing Polymer Micelles. Pd-Containing
Polymer Micelle (4). Copolymer (2, 500 mg) and Pd(PPh (500 mg,
.43 mmol) were dissolved in DCM (10 mL), and t-AmOH (50 mL)
w n
/M ) 1.64 (gel permeation chromatography).
3 4
)
0
was then slowly added. The mixture was stirred for 8 h at room
temperature to form polymer micelles. The micelle solution was heated
for 5 h at 120 °C in a sealed tube to cross-link the polymer side chain,
and then the micelle solution was poured into MeOH. The precipitate
was collected by filtration and dried to afford Pd-containing spherical
polymer micelle (4, 534 mg, Pd ) 0.81 mmol/g).
7
640).
X-ray Absorption Fine Structure. X-ray absorption experiments
2
6
were carried out on the beam line 10B at the Photon Factory at the
High Energy Accelerator Research Organization Institute of Materials
Structure Science (KEK-PF), Tsukuba, Japan, with a ring energy of
Pd-Containing Polymer (5), Cross-Linked by Microwave Ir-
radiation. Copolymer (2, 50 mg) and Pd(PPh ) (50 mg, 0.04 mmol)
3 4
2
.5GeV and stored current of 450-380 mA. X-ray absorption spectra
were recorded in a transmission mode at room temperature with a Si-
311) channel cut monochromator. The intensities of the incident and
were dissolved in DCM (1 mL), and t-AmOH (5 mL) was then slowly
added. The mixture was stirred for 8 h at room temperature to form
polymer micelles. The micelle solution was heated at 120 °C for 1 h
in a sealed tube by MW irradiation, and the mixture was then poured
into MeOH. The precipitates were collected by filtration and dried to
afford Pd-containing polymer (5, 24.9 mg, Pd ) 1.73 mmol/g).
Pd-Containing Polymer Micelle (6a). Copolymer (2, 2.0 g) and
(
transmitted X-ray were measured with a 17-cm ion chamber with an
Ar gas flow and a 62-cm ion chamber with an Ar gas flow, respectively.
Energy calibration was carried out using the Pd K-edge of a Pd foil.
The nonlinear curve-fitting analysis was performed for the Fourier-
filtered EXAFS.
3 4
Pd(PPh ) (2.0 g, 1.72 mmol) were dissolved in THF (40 mL), the
Preparation of Vinyl Monomer. 3-Bromo-2-phenylpropene.27 The
mixture of 2-phenylpropene (22.4 g, 190 mmol), NBS (23.7 g, 133
mmol), and bromobenzene (76 mL) was rapidly heated in an oil bath
at 160 °C until the NBS was dissolving. After cooling to room
temperature, the precipitate was removed by filtration and washed with
chloroform. The filtrate was purified by distillation (bp 80-85 °C/3
mmHg) to afford 3-bromo-2-phenylpropene containing 1-bromo-2-
phenylpropene (15.5 g). The purity was found to be 78.0% (determined
mixture was stirred for 8 h at room temperature, and then hexane (120
mL) was added slowly. The precipitates were collected by filtration
and dried, and then the solid was heated for 2 h at 120 °C without
solvents. The resulting solid was washed with THF and DCM,
successively, and the insoluble Pd-containing solid (6a, 1.90 g, Pd )
0
.65 mmol/g) was obtained.
Pd-Containing Polymer Micelle (6b). Copolymer (2, 500 mg) and
Pd(PPh ) (500 mg, 0.43 mmol) were dissolved in DCM (10 mL), the
3 4
1
1
by H NMR). H NMR (CDCl
s, 1H), 7.33-7.51 (m, 5H); 13C NMR (CDCl
28.3, 128.5, 137.6, 144.2.
-[(2-Phenylallyloxy)methyl]oxirane. To sodium hydride (60% in
3
) δ ) 4.39 (s, 2H), 5.49 (s, 1H), 5.56
mixture was stirred for 8 h at room temperature, and then MeOH (30
mL) was added slowly. The precipitates were collected by filtration
and dried, and then the solid was heated for 2 h at 120 °C without
solvents. The resulting solid was washed with THF, NMP, and DCM,
successively, and the insoluble Pd-containing solid (6b, 440 mg, Pd )
0.62 mmol/g) was obtained.
(
3
) δ ) 34.2, 117.2, 126.1,
1
2
mineral oil, 1.6 g, 40 mmol) suspended in dry DMF (75 mL) was added
glycidol (7.4 g, 100 mmol) in DMF (5 mL) at 0 °C. Then the solution
of 3-bromo-2-phenylpropene (78% purity, 5.05 g, 20 mmol) in DMF
Pd-Containing Polymer Micelle on Glass (9). Copolymer (2, 200
3 4
mg) and Pd(PPh ) (200 mg, 0.17 mmol) were dissolved in DCM (20
mL), and t-AmOH (100 mL) was slowly added to this mixture to form
polymer micelles. To this solution, glass (microscope cover glass,
(
26) Nomura, M.; Koyama, A. KEK Rep. 1989, 89-16, 21.
(
27) (a) Reed, S. F., Jr. J. Org. Chem. 1965, 30, 3258. (b) Vaccher, C.; Berthelot,
P.; Flouquet, N.; Vaccher, M.-P.; Debaert, M. Synth. Commun. 1993, 23,
6
71-679.
borosilicate glass (SiO
2
2 2 2
64.2%, B O 8.9%, Na O 7.2%, ZnO 7.1%, K O
J. AM. CHEM. SOC.
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VOL. 127, NO. 7, 2005 2133