Tuning Metal–Metal Distances in Nanopatterns
FULL PAPER
1
3
CH=O), 11.46 (s, 1H; OH) ppm; C NMR (CDCl
8.9, 29.2, 31.74, 68.54, 101.0, 108.7, 115.0, 135.1, 164.5, 166.4, 194.3 ppm;
elemental analysis calcd (%) for C19 : C 71.91, H 8.79; found: C
1.66, H 8.98.
3
): d=14.1, 22.6, 25.9,
mixture was stirred for 1 h under reflux and then left to cool to room
temperature. A solid precipitated during the reaction, and this was fil-
tered off, washed with ethanol and dried in vacuo to yield the pure green
2
30 3
H O
À1
7
product. Yield: 133.9 mg (0.17 mmol, 64%); IR (KBr): n˜ =1612 cm (C=
Synthesis of 4-(n-dodecyloxy)-2-hydroxybenzaldehyde (Sa2): 2,4-Dihy-
droxybenzaldehyde (5.00 g, 36.2 mmol), n-dodecyl bromide (9.02 g,
O); elemental analysis calcd (%) for C30
found: C 64.34, H 7.51.
6
H42CuO : C 64.09, H 7.53;
3
(
6.2 mmol) and KHCO
100 mL) for 3 h under reflux. The mixture was then left to cool to room
temperature and poured into an aqueous solution of hydrochloric acid
6n, 150 mL). The precipitate formed was filtered off and purified by
column chromatography (silica; n-hexane/ethyl acetate, 9:1) to yield a
3
(3.63 g, 36.2 mmol) were stirred in DMF
Synthesis of complex Cu2: The reaction was performed according to the
methodology described for complex Cu1 with solutions of copper(ii) ace-
tate monohydrate (64.1 mg, 0.32 mmol) in a mixture of ethanol and
(
water (1:1, 6 mL) and Sa2 (180.5 mg, 0.59 mmol) in ethanol (10 mL);
À1
0
.5 h reflux. Yield: 34.6 mg (0.05 mmol, 16%); IR (KBr): n˜ =1626 cm
1
white solid. Yield: 2.60 g (8.5 mmol, 23%); H NMR (CDCl
3
): d=0.86 (t,
(
C=O); elemental analysis calcd (%) for C38
H
58CuO
6
: C 67.68, H 8.67;
3
J=6.9 Hz, 3H; CH
3
), 1.22–1.35 (m, 16H; CH
2
), 1.39–1.46 (m, 2H; CH ),
2
found: C 67.80, H 8.60.
3
4
1
2
8
.74–1.81 (m, 2H; CH
.3 Hz, 1Harom), 6.50 (dd, J 8.6 Hz, J=2.3 Hz, 1Harom), 7.39 (d, J=
2
), 3.98 (t, J=6.6 Hz, 2H; OCH ), 6.39 (d, J=
2
Synthesis of complex Cu3: The reaction was performed according to the
methodology described for complex Cu1 with solutions of copper(ii) ace-
tate monohydrate (32 mg, 0.16 mmol) in ethanol (1.5 mL) and Sa4
3
=
4
3
1
3
.6 Hz, 1Harom), 9.68 (s, 1H; CH=O), 11.45 (s, 1H; OH) ppm; C NMR
): d=14.1, 22.7, 25.9, 28.9, 29.3, 29.5–29.6, 31.9, 68.6, 101.1, 108.8,
15.0, 135.2, 164.6, 166.5, 194.3 ppm; elemental analysis calcd (%) for
: C 74.47, H 9.87; found: C 74.34, H 9.94.
(
CDCl
3
(
6
103 mg, 0.34 mmol) in ethanol (1.5 mL). Yield: 72 mg (0.11 mmol,
7%); IR (KBr): n˜ =1627 cm (C=O); elemental analysis calcd (%) for
1
À1
19 30 3
C H O
C
38
H
58CuO
6
: C 67.68, H 8.67; found: C 67.68, H 8.64.
Synthesis of complex Pd1: A solution of palladium(ii) acetate (65.6 mg,
.29 mmol) in a mixture of ethanol and water (1:1, 6 mL) was added to a
Synthesis of 4-(n-hexadecyloxy)-2-hydroxybenzaldehyde (Sa3): The syn-
thesis of Sa3 was carried out as for Sa2 but with 2,4-dihydroxybenzalde-
hyde (3.00 g, 21.7 mmol), n-hexadecyl bromide (6.63 g, 21.7 mmol) and
KHCO (2.17 g, 21.7 mmol) in DMF (75 mL). The reaction mixture was
3
poured into an aqueous solution of hydrochloric acid (6n, 100 mL) and
separated by column chromatography (silica; n-hexane/ethyl acetate,
0
solution of Sa2 (177.5 mg, 0.58 mmol) in ethanol (6.5 mL). The mixture
was stirred for 1 h under reflux and then left to cool to room tempera-
ture. The solid precipitate formed was filtered off, washed thoroughly
1
3
with H O and ethanol and dried in vacuo to yield the solid green prod-
4
6
1
2
8
:1). Yield: 2.35 g (6.5 mmol, 30%); H NMR (CDCl
.9 Hz, 3H, CH ), 1.20–1.35 (m, 24H; CH ), 1.38–1.46 (m, 2H; CH
.73–1.80 (m, 2H; CH
.0 Hz, 1Harom), 6.50 (dd, J=8.6 Hz, J=2.0 Hz, 1Harom), 7.39 (d, J=
3
): d=0.86 (t, J=
2
1
uct. Yield: 131.0 mg (0.18 mmol, 62%); H NMR (CDCl
3
) d=0.86 (t,
3
2
2
),
3
3
4
3 2 2
J=6.9 Hz, 6H; CH ), 1.18–1.48 (m, 36H; CH ), 1.75 (m, 4H; CH ), 3.93
(t, J=6.6 Hz, 4H; OCH ), 6.27 (dd, J=8.8 Hz, J=2.3 Hz, 2H), 6.45 (d,
J=2.3 Hz, 2Harom), 7.21 (d, J=8.8 Hz, 2Harom), 7.90 (s, 2H; CH=O)
ppm; IR (KBr): n˜ =1623 cm (C=O); elemental analysis calcd (%) for
2
), 3.98 (t, J=6.6 Hz, 2H; OCH
2
), 6.39 (d, J=
3
3
4
3
4
3
2
4
3
1
3
.6 Hz, 1Harom), 9.68 (s, 1H; CH=O), 11.46 (s, 1H; OH) ppm; C NMR
CDCl ): d=14.1, 22.7, 25.9, 28.9, 29.3, 29.4, 29.5, 29.6–29.7, 31.9, 68.6,
01.0, 108.8, 115.0, 135.2, 164.5, 166.5, 194.3 ppm; elemental analysis
: C 76.20, H 10.56; found: C 76.02, H 10.49.
À1
(
1
3
38 58 6
C H O Pd: C 63.63, H 8.15; found: C 62.69, H 8.10.
calcd (%) for C23
H
38
O
3
Synthesis of complex Pd2: KOH (25.0 mg, 0.45 mmol) and palladium(ii)
acetate (46.0 mg, 0.20 mmol) were added to a solution of Sa3 (153.0 mg,
0.42 mmol) in ethanol (7 mL). The mixture was stirred for 3 h under
reflux and then left to cool to room temperature. The solid precipitate
Synthesis of 5-(n-dodecyloxy)-2-hydroxybenzaldehyde (Sa4): A mixture
of hydroquinone (20.10 g, 183 mmol), n-dodecyl bromide (34.50 g,
1
38 mmol) and NaOH (5.50 g, 138 mmol) in ethanol (150 mL) was vigo-
rously stirred at reflux under argon for 6 h. The mixture was then left to
cool to room temperature. The white precipitate formed was filtered off
2
formed during the reaction was filtered off, washed thoroughly with H O
and ethanol and dried in vacuo to yield the green product. Yield: 65.5 mg
1
3
and identified as the bis
A
C
H
T
R
E
U
N
G
(alkoxy) side product. Addition of H
2
O to the su-
(0.08 mmol, 42%); H NMR (CDCl
3
) d=0.86 (t, J=6.9 Hz, 6H; CH
3
),
3
pernatant led to the precipitation of the crude monoalkoxy product,
which was filtered off. The solid was recrystallised from n-hexane,
washed with water and dried in vacuo to yield white needles of 4-(n-do-
1.18–1.48 (m, 52H; CH
2
), 1.75 (m, 4H; CH
2
), 3.93 (t, J=6.6 Hz, 4H;
3
4
4
OCH ), 6.27 (dd, J=8.8 Hz, J=2.3 Hz, 2Harom), 6.45 (d, J=2.3 Hz,
2
3
2Harom), 7.21 (d, J=8.8 Hz, 2Harom), 7.90 (s, 2H; CH=O) ppm; IR
1
À1
decyloxy)phenol. Yield: 15.74 g (56.5 mmol, 41%); H NMR (CDCl
3
):
(KBr): n˜ =1623 cm
(C=O); elemental analysis calcd (%) for
3
d=0.86 (t, J=6.8 Hz, 3H; CH
3
), 1.22–1.34 (m, 16H), 1.38–1.45 (m, 2H),
.69–1.76 (m, 2H), 3.87 (t, J=6.6 Hz, 2H; OCH ,), 4.40 (s, 1H; OH),
): d=14.1, 22.7, 26.0, 29.3, 29.4,
46 74 6
C H O Pd: C 66.61, H 8.99; found: C 66.86, H 9.10.
3
1
6
2
2
Synthesis of complex Cu4: A solution of Sa1 (185 mg, 0.74 mmol) in a
solution of ammonia in methanol (7n, 7 mL) was stirred for 0.5 h under
reflux. A solution of copper(ii) acetate monohydrate (72 mg, 0.36 mmol)
in ethanol (7 mL) was then added. The mixture was stirred for 0.5 h and
then left to cool to room temperature. The precipitate formed was fil-
tered off, washed with methanol and dried in vacuo to yield the green
1
3
.75 (m, 4Harom) ppm; C NMR (CDCl
3
9.6–29.7, 31.9, 68.8, 115.6, 116.0, 149.3, 153.4 ppm.
4
-(n-Dodecyloxy)phenol (2.00 g, 7.2 mmol) was then treated with hexam-
ethylenetetramine (2.80 g, 20.0 mmol) in trifluoroacetic acid (10 mL).
The suspension was vigorously stirred for 14 h at 1008C and for a further
5
0 h at room temperature. At the end of this period an aqueous solution
of hydrochloric acid (4n, 10 mL) was added and the mixture extracted
with CH Cl and hexane. The combined organic layers were washed with
an aqueous solution of hydrochloric acid (4n), H O and a saturated
À1
solid product. Yield: 129 mg (0.23 mmol, 64%); IR (KBr): n˜ =1612 cm
(
C=N); elemental analysis calcd (%) for C30
4 2
H44CuO N : C 64.32, H 7.92,
2
2
N 5.00; C 64.23, H 7.95, N 5.00.
2
Complexes Cu5–Cu7 were synthesised according to the methodology de-
scribed for complex Cu4.
aqueous solution of NaCl. The organic layer was concentrated in vacuo,
and the obtained black oil was purified by column chromatography
Synthesis of complex Cu5: Synthesised from Sa2 (150 mg, 0.49 mmol) in
a solution of ammonia in methanol (7n, 3 mL) and copper(ii) acetate
(
0
CH
2
6
9
2
1
silica; hexane/ethyl acetate, 9:1) to yield the yellow solid product. Yield:
1
3
.40 g (1.3 mmol, 18%); H NMR (CDCl
3
): d=0.86 (t, J=6.8 Hz, 3H;
), 1.72–1.79 (m,
monohydrate (49 mg, 0.25 mmol) in a solution of ammonia in methanol
3
), 1.22–1.35 (m, 16H; CH ), 1.39–1.46 (m, 2H; CH
2
2
À1
3
3
(
7n, 1 mL). Yield: 90 mg (0.13 mmol, 55%); IR (KBr): n˜ =1617 cm
H; CH
2
4
), 3.91 (t, J=6.6 Hz, 2H; OCH
2
), 6.89 (d, J=9.1 Hz, 1Harom),
3
4
.97 (d, J=3.0 Hz, 1Harom), 7.12 (dd, J=9.1 Hz, J=3.0 Hz, 1Harom),
(C=N); elemental analysis calcd (%) for C38
H
60CuN
2
O
4
: C 67.87, H 8.99,
1
3
.82 (s, 1H; CH=O), 10.62 (s, 1H; OH); C NMR (CDCl
3
): d=14.1,
N 4.17; found: C 67.76, H 9.04, N 3.96.
2.7, 26.0, 29.2, 29.3, 29.4, 29.5–29.6, 31.9, 68.9, 116.1, 118.6, 120.0, 125.8,
Synthesis of complex Cu6: Synthesised from
a
solution of Sa3
À1
52.2, 155.9, 196.1 ppm; IR (KBr): n˜ =1671 cm (C=O); elemental analy-
(163.93 mg, 0.45 mmol) in ethanol (7 mL) and copper(ii) acetate monohy-
drate (47 mg, 0.24 mmol) in a solution of ammonia in methanol (7n,
sis calcd (%) for C19
Synthesis of complex Cu1: A solution of copper(ii) acetate monohydrate
53.8 mg, 0.27 mmol) in a mixture of ethanol and water (1:1, 14 mL) was
added to a solution of Sa1 (135.5 mg, 0.54 mmol) in ethanol (5 mL). The
30 3
H O : C 74.47, H 9.87; found: C 74.02, H 9.83.
À1
7 mL). Yield: 35.0 mg (0.04 mmol, 19%); IR (KBr): n˜ =1616 cm (C=
(
N); elemental analysis calcd (%) for C46
3.57; found: C 70.61, H 9.70, N 3.53.
H
76CuO
4
N
2
: C 70.41, H 9.76, N
Chem. Eur. J. 2006, 12, 3847 – 3857
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3855