Oligo(p-phenylenevinylene–Perylene Bisimide
FULL PAPER
mine (0.13 g, 1.50 mmol, 1.2 equiv), and Zn
A
2H; CHCH2), 3.31 (t, 2H; CH2NCO), 4.16 (t, 2H; NCH2), 5.00 (m, 1H;
NCH), 7.03 (s, 4H; ArH), 7.35 (t, 2H; ArH), 8.34 (s, 2H; ArH), 8.62 (2d,
2H; ArH), 9.67 ppm (2d, 2H; ArH).
were dissolved in dry N,N-dimethylacetamide (35 mL). The solution was
degassed with N2 for a period of 30 min and then placed in an argon at-
mosphere. The reaction mixture was refluxed for 3 h. After cooling to
room temperature, the remaining starting compound was precipitated in
diethyl ether, the solution was filtered, and the ether layer evaporated to
dryness. The remaining solid was purified extensively by column chroma-
tography (SiO2, pentane/dichloromethane 2:3) yielding pure 1 (300 mg,
2-Amino-4-{5-[9,10-(1-ethylpropylimidodicarbonyl)-1,7-bis(3,5-di-tert-bu-
tylphenoxy)perylene-3,4-dicarboximido]pentylureido}-6-[(E,E,E)-4-(4-{4-
[3,4,5-tris(dodecyloxy)styryl]-2,5-bis[(S)-2-methylbutoxy]styryl}-2,5-
bis[(S)-2-methylbutoxy]styryl)phenyl]-s-triazine
(OPV4UT-PERY):
OPV4T (0.3 g, 0.22 mmol) was dissolved in dry pyridine (2 mL) under
argon and refluxed. A solution of 3 (0.205 g, 0.21 mmol) in dry pyridine
(2 mL) was added and the mixture was concentrated to ꢂ2 mL by open-
ing the reaction vessel. After stirring for 16 h, the solvent was removed
in vacuo and the mixture purified by chromatography (SiO2, dichlorome-
thane, then dichloromethane/ethanol 98.5:1.5). After precipitation in
methanol and size-exclusion chromatography (Bio-Beads S-X1, THF)
pure OPV4UT-PERY (80 mg, 0.034 mmol, 15%) was obtained as a red
1
0.34 mmol, 28%) as a red solid. H NMR: d=0.90 (t, 6H; CH2CH3), 1.35
(s, 18H; CACHTREUNG(CH3)3), 1.36 (s, 18H; CACHRTE(UGN CH3)3), 1.91 (m, 2H; CH2), 2.21 (m,
2H; CH2), 4.99 (m, 1H; CH), 7.02 (d, 2H; ArH) 7.04 (d, 2H; ArH), 7.38
(2t, 2H; ArH), 8.29 (s, 1H; ArH), 8.35 (s, 1H; ArH), 8.59 (d, 1H; ArH),
8.63 (d, 1H; ArH), 9.66 (d, 1H; ArH), 9.69 ppm (d, 1H; ArH); 13C
NMR: d=11.6, 25.2, 31.62, 31.64, 35.4, 58.0, 114.4, 114.8, 117.6, 119.0,
120.10, 120.12, 122.1, 123.3, 124.97, 125.02, 127.1, 128.7, 129.5, 129.6,
129.7, 130.2, 132.1, 132.7, 135.3, 154.1, 154.2, 154.5, 154.6, 155.8, 156.9,
159.8, 159.9 ppm; IR: n˜ =2962, 2906, 2872, 1773, 1734, 1704, 1663, 1603,
1590, 1570, 1514, 1476, 1461, 1407, 1364, 1344, 1318, 1292, 1258, 1229,
1195, 1163, 1119, 1085, 1057, 1018, 948, 920, 900, 878, 870, 855, 809, 750,
707, 667 cmꢀ1; MALDI-TOF MS (869.43): m/z: 870.43 [M+H]+; elemen-
tal analysis calcd (%) for C57H59NO7: C 78.68, H 6.83, N 1.61; found: C
77.57, H 6.88, N 1.57.
1
solid. H NMR: d=0.86–0.95 (m, 15H; (CH2)8CH3, NCHCH2CH3), 0.99–
1.04 (m, 12H; CHHCH3), 1.10–1.17 (m, 12H; CHCH3), 1.28–1.56 (m,
90H; (CH2)8CH3, CHHCH3,
1.43–1.56 (m, 6H; OCH2CH2CH2), 1.58–2.00 (m, 20H; CHHCH3,
OCH2CH2, CHCH3, NCH2A(CH2)2CH2CH2NCON, NCHCH2CH3), 2.12–
CACHTUERGN(CH3)3, NCH2ACTHERU(GN CH2)2CH2CH2NCON),
CTHREUNG
2.17 (m, 2H; NCHCH2CH3), 3.32 (t, 2H; CH2NCON), 3.87–4.05 (m,
14H; OCH2), 4.16 (t, 2H; NCH2), 4.96 (m, 1H; NCH), 5.30 (br, 1H;
ArNHH), 6.75 (s, 2H; ArH), 6.99 (s, 2H; ArH), 7.03 (s, 2H; ArH), 7.04
(d, 1H; CH=CH), 7.09 (s, 1H; ArH), 7.11 (d, 1H; CH=CH), 7.16 (s, 1H;
ArH), 7.16 (d, 1H; CH=CH), 7.17 (d, 1H; CH=CH), 7.31 (s, 1H; ArH),
7.34 (s, 1H; ArH), 7.39 (d, 1H; CH=CH), 7.47 (s, 2H; ArH), 7.56 (d,
1H; CH=CH), 7.60 (d, 2H; ArH), 8.13 (d, 2H; ArH), 8.29 (s, 1H; ArH),
8.32 (s, 1H; ArH), 8.52 (2d, 2H; ArH), 9.19 (br, 1H; ArNHH), 9.62 (2d,
2H; ArH), 9.62 (br, 1H; NH), 9.84 ppm (br, 1H; NH); 13C NMR: d=
11.4, 11.46, 11.54, 11.6, 14.2, 16.8, 16.90, 16.92, 22.7, 24.1, 25.0, 26.2, 26.42,
26.44, 27.4, 29.0, 29.42, 29.44, 29.5, 29.68, 29.71, 29.74, 29.76, 29.79, 29.81,
30.35, 30.40, 31.2, 31.4, 31.6, 32.0, 35.0, 35.1, 35.16, 35.18, 35.20, 39.5, 40.3,
57.6, 69.1, 73.6, 74.1, 74.2, 74.4, 105.1, 109.5, 109.8, 110.5, 110.9, 114.2,
114.4, 119.3, 119.4, 121.9, 122.4, 122.5, 122.9, 123.3, 123.4, 123.5, 123.6,
124.9, 125.1, 125.7, 126.1, 126.5, 126.9, 127.3, 127.6, 128.2, 128.7, 128.8,
129.0, 129.3, 129.4, 130.0, 133.3, 133.5, 133.8, 134.2, 138.2, 142.1, 150.9,
151.1, 151.2, 151.5, 153.3, 153.7, 154.8, 155.6, 155.8, 156.1, 163.1, 163.5,
167.2, 170.2 ppm; IR: n˜ =3499, 3292, 3196, 3129, 3057, 2958, 2924, 2855,
1697, 1659, 1602, 1590, 1571, 1528, 1506, 1465, 1420, 1407, 1364, 1333,
1294, 1262, 1203, 1170, 1116, 1053, 1011, 960, 915, 900, 855, 811, 773, 753,
708 cmꢀ1. ESI-MS (2369.58): m/z: 2370.73 [M+H]+.
N,N’-Bis(1-ethylpropyl)-1,7-bis(3,5-di-tert-butylphenoxy)perylene-
3,4:9,10-tetracarboximide (1b): This molecule was obtained as a side-
product in the synthesis of 1, along with the 1,6 regioisomer(*) (~15%).
It was used as a reference compound for optical studies. 1H NMR: d=
0.92 (t, 12H; CH2CH3), 1.37 (s, 36H; CACHTRE(UNG CH3)3), 1.93 (m, 4H; CH2), 2.22
(m, 4H; CH2), 5.02 (m, 2H; CH), 7.06 (d, 2H; ArH), 7.38 (t, 2H; ArH),
8.36 (8.26*) (s, 2H; ArH), 8.61 (8.69*) (d, 2H; ArH), 9.65 (9.60*) ppm
(d, 2H; ArH); 13C NMR: d=11.2, 24.9, 31.3, 35.1, 57.5, 114.4, 119.4,
122.2, 123.1, 123.3, 123.7, 125.0, 128.6, 129.2, 130.0, 133.4, 153.6, 154.5,
155.8 ppm; IR: n˜ =2962, 2907, 2875, 1698, 1657, 1600, 1588, 1571, 1514,
1479, 1460, 1421, 1407, 1380, 1363, 1344, 1327, 1318, 1293, 1259, 1247,
1218, 1201, 1188, 1148, 1119, 1057, 1027, 1012, 1002, 954, 926, 916, 900,
858, 831, 811, 787, 750, 707, 660 cmꢀ1; MALDI-TOF MS (938.52): m/z:
938.58 [M]+; elemental analysis calcd (%) for C62H70N2O6: C 79.29, H
7.51, N 2.98; found: C 78.91, H 7.54, N 2.93.
N-(1-Ethylpropyl)-N’-5-aminopentyl-1,7-bis(3,5-di-tert-butylphenoxy)per-
ylene-3,4:9,10-tetracarboximide (2): Compound 1 (280 mg, 0.32 mmol),
1,5-pentanediamine (0.33 g, 3.22 mmol), and ZnCAHTRE(UGN OAc)2 (0.12 g,
0.64 mmol) were dissolved in dry N,N-dimethylacetamide (4 mL). The
solution was degassed with N2 for 10 min and then placed in an argon at-
mosphere. The mixture was subsequently stirred at 508C for 2 h and after
cooling to room temperature, the solvent was removed in vacuo. Pure 2
(200 mg, 0.21 mmol, 65%) was obtained after column chromatography
(SiO2, dichloromethane then dichloromethane/methanol 95:5). 1H NMR:
Scanning tunneling microscopy: All STM experiments were performed at
room temperature and under ambient conditions. The STM images pre-
sented here were obtained at the liquid/solid interface using a Discoverer
scanning tunneling microscope (Topometrix Inc., Santa Barbara, CA)
along with an external pulse/function generator (model HP 8111A).
Low-current experiments were performed using a multimode Nanoscope
IV instrument (Digital Instruments Co., Santa Barbara, CA). STM tips
were electrochemically etched from Pt/Ir wire (80/20, diameter 0.2 nm) in
an aqueous 2n KOH/6n NaCN solution. Highly oriented pyrolytic graph-
ite (HOPG; grade ZYB, advanced Ceramics Inc., Cleveland, OH) was
d=0.84 (t, 6H; CH2CH3), 1.30 (s, 36H;
CACHTRE(UNG CH3)3), 1.41 (m, 2H;
NCH2CH2CH2), 1.57 (m, 2H; CH2CH2NH2), 1.71 (m, 2H; NCH2CH2),
1.86 (m, 2H; CHCH2), 1.97, (s, 2H; NH2), 2.15 (m, 2H; CHCH2), 2.72 (t,
2H; CH2NH2), 4.12 (t, 2H; NCH2), 4.95 (m, 1H; CH), 7.00 (s, 4H;
ArH), 7.33 (2t, 2H; ArH), 8.31 (s, 2H; ArH), 8.58 (2d, 2H; ArH),
9.65 ppm (2d, 2H; ArH); 13C NMR: d=10.4, 23.0, 23.9, 26.3, 26.8, 28.7,
30.4, 34.1, 38.5, 39.1, 56.6, 113.2, 118.4, 120.6, 121.4, 121.8, 122.0, 122.3,
123.0, 123.4, 123.8, 127.5, 127.8, 128.8, 131.9, 132.3, 152.6, 152.7, 153.4,
153.5, 154.5, 154.8, 161.6, 162.1 ppm; IR: n˜ =3387, 3166, 3068, 2962, 2873,
1698, 1657, 1601, 1589, 1514, 1459, 1420, 1407, 1363, 1332, 1293, 1262,
used as the substrate.
A drop of a solution of OPV4UT-PERY
(0.5 mgmLꢀ1) in 1,2,4-trichlorobenzene (Aldrich) was applied to a freshly
cleaved surface of HOPG. STM images were acquired in the variable cur-
rent mode by scanning the STM tip immersed in solution at a negative
sample bias (electrons tunnel from the sample to the tip). The measured
tunneling currents were converted into a gray scale: black (white) refers
to a low (high) measured tunneling current. After successful imaging of
the monolayer, an atomically resolved image of the graphite substrate
was recorded at exactly the same location with identical scanning param-
eters except for the sample bias. The images were corrected for scanner
drift by using SPIP software.[34] (Image Metrology ApS) with graphite as
the calibration grid. Only images containing a small drift were used for
analysis.
1213, 1202, 1188, 1118, 1057, 956, 899, 871, 856, 811, 753, 708 cmꢀ1
;
MALDI-TOF MS (953.53): m/z: 954.62 [M+H]+.
N-(1-Ethylpropyl)-N’-(5-isocyanatopentyl)-1,7-bis(3,5-di-tert-butylphe-
noxy)perylene-3,4:9,10-tetracarboximide (3): Di-tert-butyl tricarbonate
(68 mg, 0.26 mmol) was dissolved in dry dichloromethane (6 mL) under
argon. A solution of 2 (0.2 g, 0.21 mmol) in dry dichloromethane (13 mL)
was added dropwise and the resulting mixture was stirred for 10 min
after which the solvent was evaporated in vacuo. FTIR spectroscopy re-
vealed the formation of the corresponding isocyanate 3 (n˜ =2274 cmꢀ1),
which was used without further purification. 1H NMR: d=0.89 (t, 6H;
CH2CH3), 1.34 (s, 36H; C
ACTHREU(GN CH3)3), 1.49 (m, 2H; NCH2CH2CH2), 1.63–
1.81 (m, 4H; CH2CH2NCO, NCH2CH2), 1.90 (m, 2H; CHCH2), 2.20 (m,
Chem. Eur. J. 2006, 12, 9046 – 9055
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9053