6
L. J. TꢀꢁꢂAN ANꢃ X. ZHꢄNꢅ
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1
IR spectroscopy
2850(CHO), 2726(CHO), 1699, 1460, 1377 cm ꢂALꢃI-TOF:
a series of peaks separated by 102 and 132 mass units. ꢅPC:
Mn = 14,150, Mw = 26,400.
Infrared spectra were recorded on a Perkin-ꢄlmer spec-
trum RX I FT-IR system in Nujol, potassium bromide discs,
chloroform or using an ATR ꢃuraSampIR II diamond
press.
Synthesis of porphyrin cross-linked polymer 2
1.00 g of copolymer 1 (styrene/3-vinylbenzaldehyde = 5:1),
Mass spectrometry
ꢂatrix-assisted laser desorption ionisation time of flight
benzaldehyde (0.63 mL, 6.2 mmol) and distilled pyrrole
(0.53 mL, 7.6 mmol) were added to 25 mL of propionic in
a round bottomed flask. The solution was heated to reflux
for one and half hours. The solution was left to cool to room
temperature and filtered through Büchner funnel. The
solid was washed with cold methanol and water several
times. The free porphyrin can be removed through wash-
ing solid with THF several times. The dark black solid prod-
uct was obtained after vacuum drying for 2 days. ꢁield:
(
ꢂALꢃI-TOF) mass spectrometry was carried out using
dihydroxybenzoic acid as the matrix on a Bruker Reflex III
mass spectrometer with a mass range of 200–500,000 ꢃa.
Elemental analysis
C, H and N proportions were determined using a
Perkinꢄlmer 2400 CHNS/O Series II ꢄlemental Analyzer.
1
3
1
.12 g (75%), C solid-state NꢂR (ppm): δ 40–50 (CHCH )
2
Gel permeation chromatography
ꢅPC was carried out using THF as eluent with water 515
HPLC pump, ꢅilson 234 autoinjector and 30-cm Pl gel,
100–110 (Ar–C, porphyrin), 128 (Ar–C, polymer + por-
phyrin), 146 (Ar–C, polymer + porphyrin), solid-state UV/
vis (nm) λmax: 433, 517, 550, 588, 649. ꢄlemental analysis:
found C: 87.37%, H: 6.75%, N: 2.79%. Porphyrin content:
10-μm ꢂixed-B columns (1.00 mL/min) at room temper-
−1
ature. ꢃetection was by refractive index using an ꢄrma
ꢄRC-7512 RI detector. The system was calibrated using
polystyrene standards and the results were analysed by
Cirrus ꢅPC-online software.
0.51 mmol g .
Synthesis of the iron porphyrin cross-linked polymer 3
A fine powder of porphyrin cross-linked polymer 0.2 g
(0.2 mmol of porphyrin included) was added to a three-
Gas chromatography
ꢅas chromatography results were obtained on Perkinꢄlmer
Autosystem XL gas chromatography system. Samples were
neck round bottomed flask connected with a condenser.
The reaction flask was evacuated and flushed with nitro-
gen. Anhydrous THF 20 mL and 2,6-lutidine 0.12 mL
(1.0 mmol) were added by syringe. The reaction was then
heated to reflux for 15 min, after which anhydrous FeCl2
(250 mg, 2 mmol) was added and the solution refluxed for
another 16 h. After cooling the reaction to room tempera-
ture, the mixture was exposed to air with stirring for 30 min
to ensure complete oxidation to the Fe(III) complex. After
filtration and washing several times withTHF, the dark solid
product was collected and dried under vacuum for 24 h.
Solid-state UV/vis (nm): 420, 530, 590.
carried out with H gas flow in Alltech AT1 nonpolar col-
2
umn (length 30 m, Iꢃ: 0.32 mm, film thickness 5.00 μm).
The injection temperature was 250 °C and oven temper-
ature was 50 °C for 5 min and then increased from 50 to
250 °C over 20 min. Product yields were calculated using
the peak areas from iodobenzene (as an internal reference
for total oxidations) and the corresponding epoxide stand-
ards. The epoxides required for calibration were synthe-
sised according to a literature procedure (using mCPBA)
and the products characterised and compared with the
Preparation of iodosylbenzene 4
3
ꢂ sodium hydroxide (15 mL) was added over 3 min to
Synthesis of a styrene and 3-vinylbenzaldehyde
copolymer 1
Freshly distilled styrene (2.08 g, 20 mmol) and 3-
vinylbenzaldehyde (0.53 g, 4 mmol) were added to 20 mL
of dried toluene. 2,2'-azobisisobutyronitrile (91 mg 2.3 mol
a beaker containing (diacetoxyiodo)-benzene (3.22 g,
0.01 mol) with vigorous stirring. The reaction was then left
to stand for a period of 45 min. ꢃistilled water (15 mL) was
then added with continual stirring and the solid collected
via vacuum filtration. The solid was then stirred in excess
distilled water for a period of 30 min and the solid was col-
lected. The final step of purification was performed by stir-
ring the collected yellow solid in chloroform for a period
of 30 min. The titled product was collected via vacuum fil-
tration and dried in a vacuum desiccator. ꢁield 1.47 g, 67%,
%) was then added and the solution was degassed via 3
freeze/thaw cycles. The solution was then heated to 70 °C
for 24 h. The copolymer was obtained after precipitation
from methanol and drying under vacuum for 24 h. ꢁield:
1
1
.38 g (53%) H NꢂR (CꢃCl , ppm): δ 1.26 (m, CH–CH2)
3
1
1
.73 (m, CH–CH ), 6.55 (m, Ar–H styrene), 6.98 (m, Ar–H
HNꢂR (Cꢃ Oꢃ, 400 ꢂH ) δ 8.05 (m, 2H, Ar o-CH) 7.58 (m,
2
3
Z
H
1
3
13
benzaldehyde) 9.68 (s (brd), CHO). C NꢂR (CꢃCl , ppm):
4
3H, Ar p-CH, Ar m-CH). CNꢂR (CꢃCl , 400 ꢂH ) δ 131.9,
3 Z C
130.8, 130.6. FTIR (cm ) 3038 (aromatic C–H stretch) 1566,
3
1
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0.4, 125.7, 127.6, 127.9, 145.3. IR(KBr) ν cm : 2930,