alkaline ethanolic solution of iodine (4.07 g, 0.016 mol in 50 ml
procedures.7 1,6,7,12-Tetra-(tert-butylphenoxy)-perylene-3,4,9,10-
tetracarboxylic acid bisanhydride (1) was synthesized accord-
ing to the literature.5,8 Column chromatography was performed
on silica gel (Merck Silica Gel 60, mesh size 0.2–0.5 mm). Rf
values for analytical thin layer chromatography have been
determined on Merck TLC sheets (Silica Gel 60, F254). NMR
spectra were recorded on a Bruker DRX 400 spectrometer
using TMS as internal standard, mass spectra were taken on
Bruker SSQ 7000 (CI or FAB) and Bruker Reflex III (MALDI-
TOF, positive mode) instruments and AFM measurements
were carried out on a Digital Nanoscope III (Digital Instru-
ments Inc., Santa Barbara, CA).
5% NaOH) by heating for 15 min. The precipitate was isolated
by filtration and recrystallized from ethanol to give 4.43 g
1
(72%) of 6. H NMR (400 MHz, CDCl3, J/Hz): dH 8.20 (d, J
8.1, 4H), 6.96 (d, J 8.0, 4H), 3.99 Hz (t, J 7.5, 4H), 2.70 (t, J 7.3,
4H), 1.84 (mc, 4H), 1.69 (mc, 4H), 1.32 (mc, 24H); 13C NMR
(100 MHz, CDCl3): dC 164.1, 141.2, 125.8, 114.3, 68.8, 39.0,
29.6, 29.3, 29.3, 29.1, 29.1, 28.8, 28.8, 28.4; m/z (FAB, 3-nba):
621 [M1H]1. Elemental analysis calcd. for C32H48N2O6S2: C
61.91, H 7.79, N 4.51. Found: C 62.02, H 7.96, N 4.49.
S,S’-Bis[10-(4’-aminophenyl)decyl]-disulfide (7). Disulfide 6
(1.09 g, 1.75 mmol), graphite (2 g) and hydrazine hydrate (2 g,
0.04 mol) were stirred at 60 uC under argon-gas atmosphere for
8 h during which three additional portions of graphite (each 1 g)
and hydrazine hydrate (each 1 ml, 0.01 mol) were added. The
reaction mixture was heated overnight under reflux and the
product was extracted in a Soxhlet extractor with ethanol.
After evaporation of the solvent, 0.8 g (81%) of 7 were isolated
as a yellow powder. Mp 84–86 uC (87–88 uC)10. 1H NMR (400
MHz, CDCl3, J/Hz): dH 6.69 (d, J 8.5, 4H), 6.58 (d, J 8.5, 4H),
3.79 (t, J 6.6, 4H), 2.61 (t, J 6.5, 4H), 1.65 (t, J 7.4, 4H), 1.60
(mc, 4H), 1.24 (mc, 24H); 13C NMR (100 MHz, CDCl3): dC
152.3, 139.7, 116.3, 115.6, 68.6, 39.1, 29.4, 29.3, 29.3, 29.1, 29.1,
28.8, 28.4, 25.9; m/z (FAB, 3-nba): 561 [M1H]1, 282
2.2. Synthesis
Imide anhydride 3. Perylene bisanhydride 1 (0.55 g, 0.56
mmol), trisdodecyloxyaniline 2 (0.36 g, 0.56 mmol)9 and zinc
acetate dihydrate (0.08 g) were suspended in quinoline (30 ml)
by sonication for 20 min and heated at 180 uC for 2 h under
argon-gas atmosphere. After cooling to room temperature,
the mixture was poured into a mixture of 20 ml conc. HCl
and 130 ml methanol and the red precipitate was collected by
suction filtration. Washing with 2 6 30 ml methanol and
drying in vacuo afforded 0.87 g of a red violet solid which was
purified by column chromatography on silica (eluent: dichloro-
methane–hexane 2:1) to give three fractions containing
perylene dyes, i.e. bisimide 4 (360 mg, 29%, Rf ~ 0.42),5
imide anhydride 3 (170 mg, 19%, Rf ~ 0.36) and remaining
starting material 1 (0.11 g, 20%, Rf ~ 0.26). Compound 3 was
isolated by precipitation with methanol, centrifugation and
drying at 50 uC/1023 mbar. Mp 155–156 uC. 1H NMR
(400 MHz, CDCl3, J/Hz): dH 8.23 (s, 2H), 8.20 (s, 2H), 7.25
(mc, 8H), 6.85 (mc, 8H), 6.39 (s, 2H), 3.97 (t, J 6.6, 2H), 3.88 (t,
J 6.5, 4H), 1.75 (mc, 6H), 1.2–1.4 (m, 90H), 0.85–0.90 (m, 9H);
m/z (MALDI-TOF-MS (Bruker Reflex III, positive mode,
dithranol)): 1611.6 [M1H]1. Elemental analysis calcd. for
[M1H]21
.
Bis-perylenebisimide disulfide 8. A mixture of perylene imide
anhydride 3 (50 mg, 0.03 mmol), aniline 7 (7.25 mg,
0.013 mmol), zinc acetate dihydrate (3.22 mg, 0.015 mmol)
and quinoline (5 ml) was heated at 180 uC for 4 h under argon-
gas atmosphere. The reaction mixture was cooled to room
temperature, poured into 40 ml 1 N HCl and stirred for 20 min.
The resulting precipitate was collected and washed thoroughly
with water and methanol. Twofold column chromatography
(silica; CH2Cl2–hexane 2 : 1) of the dark blue solid afforded a
still impure perylene bisimide dye mixture which was further
purified on a Merck LOBAR MPLC column (Si 60, Size B;
CH2Cl2–hexane 80:20, flow 4 ml min21) to give 5 mg of pure 8
(10%). 1H NMR (400 MHz, CDCl3, J/Hz) dH 8.17 (s, 4H), 8.15
(s, 4H), 7.16 (dd, J 8.8, J 1.4, 16H), 7.06 (d, J 9.0, 4H), 6.91 (d, J
9.0, 4H), 6.78 (m, J 8.7, 16H), 6.33 (s, 4H), 3.91 (t, J 6.6, 8H),
3.82 (t, J 6.5, 8H), 2.60 (t, J 7.5, 4H), 1.69 (mc, 16H), 1.60 (mc,
4H), 1.35 (mc, 20H), 1.19 (mc, 184H), 0.80 (mc, 18H). m/z
(MALDI-TOF-MS (Bruker Reflex III, positive mode, dithra-
C106H133NO12: C 78.92, H 8.31, N 0.87. Found: C 78.74, H
8.21, N 0.98.
10-(p-Nitrophenoxy)-decylbromide (5). Potassium carbonate
(89.44 g, 0.65 mol) and potassium iodide (1.55 g, 0.009 mol)
were added to a solution of p-nitrophenol (10.0 g, 0.07 mol)
and 1,10-dibromodecane (43.15 g, 0.14 mol) in cyclohexanone
(500 ml) and the resulting suspension was heated to reflux
under a nitrogen-gas atmosphere for 5 h. The hot solution was
filtered and the residue was extracted with 3 6 50 ml of
cyclohexanone. The combined organic layers were concen-
trated in vacuo at 140 uC/0.2 Torr and the highly viscous brown
residue was treated with a mixture of ethanol–methanol (1:10)
to give 50 g of a yellowish powder after standing overnight.
Column chromatography of this product on silica with hexane–
nole)): 3748 [M1H]1, 1874 [M1H]21
.
2.3. Preparation of gold-patterned surfaces.
Polystyrene[1350]-block-poly-(2-vinylpyridine)[400] was dissolved
in 5 ml toluene at a concentration of 5 mg ml21 and the mixture
was stirred for 24 h before 6.21 mg HAuCl4 was added
corresponding to a loading of ca. 30% of the pyridine units.
Into this solution glass wafers (DESAG, Type D 263, D ~ 0,
175; cleaved into sizes of 1 6 2 cm and purified by sonication in
acetone, Millipore water and isopropanol) were dipped to a
depth of 1 cm and pulled out at a speed of 10 mm min21 with a
Wilhelmy balance. Thus prepared densely packed gold-loaded
micelles were exposed to a hydrogen plasma (TePla 100,
0.2 mbar, 100 W, 25 min) which removes the polymer and
reduces the gold to give a two-dimensional hexagonal lattice of
5–7 nm gold particles at a distance of 80 nm according to
AFM. The surface was further activated with an oxygen
plasma (0.2 mbar, 100 W, 10 min) and, to avoid any unspecific
adsorption of the dyes by means of dipolar interactions with
the glass wafers, treated in a glove box with a 1023 mM
solution of octadecyltrichlorosilane in dry toluene for 12 h and
rinsed several times with toluene before they were immersed
into a 1.9 6 1024 M solution of 8 in dichloromethane for 12 h.
Finally, these solutions were rinsed with dichloromethane and
1
ethylacetate (20 : 1) afforded 19.2 g (74%) of pure 5. H NMR
(400 MHz, CDCl3, J/Hz): dH 8.19 (d, J 9.3, 2H), 6.95 (d, J 9.4,
2H), 4.06 (t, J 6.5, 2H), 3.28 (t, J 7.3, 2H), 1.82 (mc, 2H), 1.48
(mc, 2H), 1.32 (mc, 12H); 13C NMR (100 MHz, CDCl3): dC
164.1, 141.2, 125.8, 114.3, 68.8, 33.9, 32.7, 30.3, 29.2, 28.8, 28.6,
28.0, 25.8, 22.7; m/z (FAB, 3-nba): 358 [M1H]1. Elemental
analysis calcd. for C16H24NO3Br: C 53.64, H 6.75, N 3.91.
Found: C 53.50, H 6.74, N 3.73.
S,S’-Bis[10-(4’-nitrophenyl)decyl]-disulfide (6). Bromide
5
(7.15 g, 0.02 mol), and thiourea (1.52 g, 0.02 mol) were
heated in ethanol (15 ml) for 3 h under reflux. The mixture was
cooled and a 9% aqueous NaOH solution (15 ml) was added.
The mixture was heated to reflux for another 2 h, cooled to
room temperature, acidified by addition of 1 N HCl and
extracted with ether (3 6 30 ml). The combined organic layers
were washed with water (2 6 15 ml) and dried over sodium
sulfate. After filtration and evaporation of the solvent 5.7 g of
an orange oil was obtained that was further reacted with an
768
J. Mater. Chem., 2003, 13, 767–772