Macromolecules
Article
79.42%; hydrogen (expected value 11.05%), found: 11.38%. ES MS:
347 (MH+). Mp: 42−44 °C.
substrate, 8 mg of PPG-TGI cross-linker, and 2.5 μmol of porphyrin-
containing catalyst and a 2 mL solution of the aqueous phase (1% w/w
aqueous solution of 125 nm PGMA50-PS particles). Homogenization
took place using an IKA Ultra-Turrax T-18 homogenizer with a 10
mm dispersing tool operating at 12 000 rpm for a period of 2 min. The
colloidosome was injected into a reaction vial via a syringe and the
suspension was then stirred in the dark for a period of 30 minutes
under an atmosphere of nitrogen. After completion, the suspension
was extracted using dichloromethane (5 mL), and the organic layer
was collected and filtered using a Whatman GD/X syringe filter with a
pore size of 0.45 μm. The filtrate was transferred into a GC vial for
analysis via manual injection.
5,10,15,20-Tetra(4-hexadececycloxyphenyl)porphyrin. Boron tri-
fluoride diethyl etherate (37.30 μL, 0.3 mmol) and a catalytic amount
of anhydrous ethanol (1.95 mL, 30 mmol) were added to a solution of
4-hexadececycloxybenzaldehyde (1.05g, 3.0 mmol) and pyrrole (210.2
μL, 3.0 mmol) in anhydrous dichloromethane (300 mL, 4.68 mol, 15.6
mol/L) at room temperature under argon. The reaction mixture was
then stirred for 1 h in an inert gas stream at room temperature; 2,3-
dichloro-5, 6-dicyano-1.4 benzoquinone (619.0 mg, 2.7 mmol) was
added, and the mixture was stirred for another 1 h. The reaction
products were separated by flash chromatography and eluted with
chloroform. The target product was purified by column chromatog-
raphy and eluted with chloroform. Yield: 1.27 g, 25%. 1H NMR
(CDCl3, 400 MHZ): δH 8.88 (s, 8H, pyrrolic β-H), 8.14 (d, 8H,
phenylic o-CH J = 8.0), 7.30 (d, 8H, phenylic m-CH J = 8.5), 4.30 (t,
8H, OCH2C15H31, J = 6.0), 2.01 (bm, 8H, OCH2CH2C14H29) 1.72−
1.23 (bm, 104H, OCH2CH2C14H26CH3), 0.91 (t, 12H, OC15H30CH3,
J = 6.5), −2.72 (s, 2H, NH). 13C NMR (CDCl3, 400 MHZ): δC 159.0,
158.3, 144.1, 135.6, 134.6, 119.9, 114.3, 112.71, 100.9, 68.4, 32.0, 29.7,
29.4, 26.3, 22.7, 14.1. FTIR (cm−1): 2918, 2850 (alkyl C−H stretch),
1509, 1241; EA %: carbon (expected value 82.28%), found 81.94%;
hydrogen (expected value 10.10%), found: 9.97%; nitrogen (expected
value 3.55%), found 3.41%. MALDI−TOF MS: 1575.4 (MH−). UV
absorbance (CHCl3): λmax (nm) 423, 520, 557, 593, 651.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We would like to thank Professor S. P. Armes and Dr. K. L.
Thompson (University of Sheffield) for technical assistance and
advice. We would also like to thank the EPSRC for funding
(G.M. and A.E.).
Synthesis of 5,10,15,20-Tetra(4-hexadececycloxyphenyl)-
porphyrin Iron(III) Complex 6. 5,10,15,20-Tetra(4-
hexadececycloxyphenyl)porphyrin (50 mg, 3.17 × 10−2 mmol) was
dissolved in THF (25 mL) with iron(II) chloride (80.4 mg, 0.634
mmol) and 2,6-lutidine (9.2 μL, 7.93 × 10−2 mmol). The solution was
warmed to 50 °C under reflux and stirred for 3 h. Solvent was then
removed via rotary evaporation and a 1:1 mix of chloroform and water
was added to the flask. After vigorous shaking many insoluble
impurities formed at the solvent interface and were removed via
vacuum filtration. The organic layer was collected and solvent was
removed via rotary evaporation and eluted through a silica column
with 1:1 chloroform and methanol. Yield: 25 mg, 50%. FTIR (cm−1):
2917, 2849 (alkyl C−H stretch), 1511 (aromatic CC stretch), 1242
(C−O). MS MALDI: 1631(MH+). UV absorbance (CHCl3): λmax
(nm) 412, 573, 616.
Synthesis of Iodosylbenzene. A 3 M sample of sodium hydroxide
(15 mL) was added over 3 min to 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. Distilled
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 collected. The
final step of purification was performed by stirring the collected yellow
solid in chloroform for a period of 30 min. The titled product was
collected via filtration and dried in a desiccator. Yield: 1.47 g, 67%.
1HNMR (CD3OD, 400 MHZ): δH 8.05 (m, 2H, Ar o-CH) 7.58 (m,
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Macromolecules XXXX, XXX, XXX−XXX