Imaging by Sensitized Photoxygenation
FULL PAPER
next step without further purification. The product was purified by flash
chromatography (hexane/EtOAc 10:1) to afford 1.27 g (66%) of the an-
thracene 7. 1H NMR (300 MHz, CDCl3, 258C, TMS): d=7.56–7.78 (m,
9H), 7.44–7.52 (m, 4H), 7.32–7.39 (m, 4H), 6.92 (dd, 3Ja =10.8 Hz, 3Jb =
17.6 Hz, 1H), 5.95 (d, 3Jb =17.6 Hz, 1H), 5.39 ppm (d, 3Ja =10.8 Hz, 1H);
13C NMR (300 MHz, CDCl3, 258C, TMS): d=139.4 (s), 139 (s), 137.5 (s),
137.1 (s), 137.0 (d), 131.9 (d), 131.7 (d), 130.2 (s), 130.2 (s), 128.7 (d),
128.7 (d) 127.8 (s), 127.3 (d), 127.2 (d), 126.6 (d), 125.4 (d), 125.3 (d),
114.5 ppm (t); elemental analysis calcd (%) for C28H20 (356.0): C 94.38,
H 5.61; found: C 93.42, H 5.66.
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Oligomerization from monomer 7 to compound 2: Monomer 7 (200 mg,
0.6 mmol) and azobisisobutyronitrile (AIBN) (5 mg) were dissolved in
anhydrous THF (10 mL) and refluxed under argon for 6 h. The precipi-
tate formed was filtered off and was dissolved in CH2Cl2. Yield of precip-
itate: 80 mg (40%). Average molecular weight (Mw): 3120 gmolÀ1; weight
1
dispersity: 2.53; H NMR (300 MHz, CDCl3, 258C, TMS): d=6.8–7.8 (br,
17H), 1.8–2.5 (br, 1H), 1.0–1.5 ppm (br, 2H).
Sample preparation: For UV/Vis absorption measurements,
1 or 2
(40 mmol, ~20 mg) were dissolved in CH2Cl2 (4 mL). Solutions of 1.6
10À3 m of the sensitizers methylene blue (MB) and meso-tetraphenylpor-
phyrin (TPP) were prepared in CH2Cl2. Aliquots of the sensitizer solu-
tions were added to the solutions of the anthracenes and a volume of
60 mL was dropped onto a glass slide. After evaporation of the solvent,
the samples were placed into a sample holder.
Imaging: Samples were prepared from either drop coating or spin coat-
ing.
Drop coating: The sensitizer solution (30 mL) was added to the anthra-
cene (20 mg) dissolved in CH2Cl2 (4 mL). An amount (60 mL) of this sol-
ution was dropped onto the glass slide and the solvent was allowed to
evaporate.
Spin coating: Films were prepared from solutions of the anthracene
(20 mg) in CH2Cl2 (1 mL) and the sensitizer solution (30 mL).
Samples were covered with a transparent film and irradiated with a 20 W
halogen lamp for 10 min at a distance of 10 cm, with a high-pass filter
with a 515 nm cut-off placed between the sample and the light source.
The sample for AFMmeasurement was obtained by irradiation through
a TEMgrid of 50 mm grid size, with a blank transparent film between the
grid and the sample.
Development: Immediately after irradiation, the samples were dipped
into hexanes for 2 min and dried in air. AFMwas carried out in tapping
mode on a glass slide.
Thermolysis: Heating of the irradiated glass slides was carried out in a
protective glass vial in an oven at constant temperature.
Acknowledgements
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We thank Anne Heilig for AFMmeasurements. Generous financial sup-
port from the Deutsche Forschungsgemeinschaft (DFG, Li 556/9-1) and
from the Graduate School “Confined Interactions and Reactions in Soft
Matter” is acknowledged.
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Received: March 17, 2006
Published online: September 27, 2006
Chem. Eur. J. 2006, 12, 9276 – 9283
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9283