N. Martꢁn, D. M. Guldi et al.
ZnP-oPPV(3)-C60 (13a): Yield: 51% 1H NMR (200 MHz, CDCl3, 258C,
TMS): d=8.96 (s, 8H; Hpyrrolic), 8.19 (d, 2H, 3J(H,H)=6.5 Hz; HAr-Porf),
8.1 (brs, 6H; HAr-Porf), 7.89 (d, 2H, 3J(H,H)=6.5 Hz; HAr-Porf), 7.8 (brs,
3H; HAr-Porf), 7.7–7.4 (m, 12H; HAr-Olig, Holef), 7.2–7.1 (m, 4H; Holef); 4.77
(d, 1H, 2J(H,H)=8.8 Hz; Hpyrrolidine), 4.70 (s, 1H; Hpyrrolidine), 4.0 (m, 5H;
CH2O, Hpyrrolidine), 2.79 (s, 3H; CH3N), 1.9 (m, 4H; CH2), 1.7–1.4 (m,
66H; CH2), 0.9 ppm (m, 6H; CH3); 13C NMR (75 MHz, CDCl3/CS2),
258C, TMS): d=155.72, 155.69,153.50, 153.27, 152.95, 152.80, 152.70,
150.88, 150.80, 150.13, 149.73, 148.16, 146.66, 146.13, 145.85, 145.73,
145.51, 145.35, 145.29, 145.15, 144.97, 144.83, 144.73, 144.57, 144.47,
144.42, 144.24, 144.11, 144.08, 143.91, 143.87, 143.77, 142.74, 142.45,
142.21, 142.12, 141.96, 141.86, 141.74, 141.48, 141.18, 141.01, 139.53,
139.28, 139.13, 137.98, 137.27, 136.35, 136.28, 135.90, 135.74, 135.01,
134.79, 132.18, 132.02, 131.81, 131.53, 129.64, 129.51, 129.39, 129.22,
128.74, 128.14, 128.08, 127.92, 126.81, 126.62, 126.45, 124.63, 123.80,
123.21, 122.27, 122.19, 120.61, 120.19, 110.12, 109.94, 83.14, 83.06, 69.13,
69.07, 39.80, 34.73, 31.63, 29.81, 29.56, 26.06, 22.88, 14.21 ppm; IR (KBr):
n˜ =2950, 2926, 2857, 1590, 1463, 1421, 1204, 1180, 1068, 1001, 797, 716,
527 cmꢁ1; UV/Vis (CH2Cl2): lmax (e)=255 (129000), 329 (61500), 403
(59000 sh), 424 (457000), 513 (7000), 550 (24000), 590 nm
(9500 molꢁ1 cm3 dmꢁ1); MS (ESI): m/z (%): 2297 (100) [M+]; elemental
analysis (%) calcd for C167H123N5O2Zn·4H2O: C 84.66, H 5.57, N 2.96;
found: C 84.23, H 5.67, N, 2.99.
16: Potassium tert-butoxide (45 mg, 0.40 mmol) was added portionwise to
a solution of 15 (150 mg, 0.30 mmol) and 7 (63 mg, 0.30 mmol) in dry
THF (20 mL), and the reaction mixture was stirred at room temperature
for 40 min under argon. After removing the solvent, the residue was dis-
solved in CHCl3 (100 mL), 1m HCl (100 mL) added, and the reaction
mixture stirred overnight. The organic phase was separated and dried
over MgSO4. Further purification was accomplished by flash chromatog-
raphy on silica gel with hexane/CH2Cl2 (1/1) to obtain 110 mg (72%) of
16 as an orange solid.
1H NMR (200 MHz, CDCl3, 258C, TMS): d=10.00 (s, 1H; CHO), 7.87
(d, 1H, 3J(H,H)=8.0 Hz; HAr), 7.66 (d, 1H, 3J(H,H)=8.3 Hz; HAr), 7.56
(d, 1H, 3J(H,H)=16.1 Hz; Holef), 7.54 (d, 2H, 3J(H,H)=8.3 Hz; HAr),
7.49 (d, 1H, 3J(H,H)=16.3 Hz; Holef), 7.39 (d, 1H, 3J(H,H)=7.5 Hz;
3
3
H
H
Ar), 7.35 (d, 1H, J(H,H)=7.5 Hz; HAr), 7.26 (d, 1H, J(H,H)=16.1 Hz;
olef), 7.16 (d, 1H, 3J(H,H)=16.1 Hz; Holef), 7.14 (s, 1H; HAr), 7.13 (s,
1H; HAr), 4.07 (m, 4H; CH2O), 1.89 (m, 4H; CH2), 1.59–1.26 (m, 12H;
CH2), 0.93 ppm (t, 6H; CH3); 13C NMR (50 MHz, CDCl3, 258C, TMS):
d=191.56, 151.53, 151.09, 144.21, 137.84, 135.19, 130.22, 129.39, 128.66,
128.05, 127.57, 127.30, 127.17, 126.82, 126.58, 125.92, 123.37, 110.98,
110.60, 69.67, 69.54, 31.62, 29.47, 29.44, 25.96, 22.64, 14.01 ppm; IR
(KBr): n˜ =2951, 2930, 2856, 1697, 1597, 1491, 1466, 1423, 1210, 1165, 964,
844, 810, 752, 690 cmꢁ1; UV/Vis (CH2Cl2): lmax (e)=246 (15400), 336
(19000), 408 nm (25600 molꢁ1 cm3 dmꢁ1); MS (EI): m/z (%): 510 (100)
[M+], 418 (10) [M+ꢁC6H13], 105 (8).
ZnP-oPPV(5)-C60 (13b): Yield: 32% 1H NMR (200 MHz, CDCl3, 258C,
TMS): d=8.97 (s, 8H; Hpyrrolic), 8.18 (d, 2H, 3J(H,H)=7.4 Hz; HAr-Porf),
8.1 (brs, 6H; HAr-Porf), 7.89 (d, 2H, 3J(H,H)=7.4 Hz; HAr-Porf), 7.8 (brs,
3H; HAr-Porf), 7.6–7.4 (m, 20H; HAr-Olig, Holef), 7.1–7.0 (m, 8H; Holef); 4.69
(d, 1H, 2J(H,H)=7.9 Hz; Hpyrrolidine), 4.58 (s, 1H; Hpyrrolidine), 4.0 (m, 4H;
Dyads 17 and 18: These two reference compounds were prepared by fol-
lowing the same synthetic methodology used for triads 13a,b with N-oc-
tylglycine[38] instead of N-methylglycine.
1
17: Yield 42%; H NMR (200 MHz, CDCl3, 258C, TMS): d=7.79 (d, 2H,
3
CH2O), 3.93 (d, 1H, J(H,H)=7.9 Hz; Hpyrrolidine), 2.75 (s, 3H; CH3N), 1.9
J(H,H)=7.0 Hz; HAr), 7.60–7.32 (m, 7H; HAr), 7.20 (d, 1H, 3J(H,H)=
16.1 Hz; Holef), 7.15 (d, 1H, 3J(H,H)=16.1 Hz; Holef), 7.12 (d, 2H,
3J(H,H)=16.1 Hz; Holef), 7.10 (s, 1H; HAr), 5.11 (d, 1H, 2J(H,H)=
(m, 4H; CH2), 1.7–1.3 (m, 66H; CH2), 1.0 ppm (m, 6H; CH3); 13C NMR
(125 MHz, CDCl3/CS2), 258C, TMS): d=155.73, 155.38, 153.10, 152.91,
152.59, 150.88, 150.57, 150.16, 149.74, 148.21, 146.58, 145.84, 145.53,
145.41, 145.24, 144.54, 144.45, 143.87, 143.68, 143.32, 142.31, 141.79,
141.29, 140.89, 139.37, 139.01, 137.37, 137.18, 137.01, 136.74, 136.52,
136.26, 136.11, 136.03, 135.69, 135.17, 134.85, 132.21, 132.11, 132.03,
131.53, 130.01, 129.67, 129.50, 129.01, 128.74, 128.55, 128.18, 128.01,
127.80, 127.72, 127.48, 127.38, 126.94, 126.86, 126.75, 126.25, 126.12,
125.02, 124.66, 123.96, 123.38, 123.24, 122.30, 122.22, 121.95, 120.63,
120.19, 110.09, 110.02, 82.89, 69.54, 69.13, 39.74, 34.76, 32.01, 31.77, 31.66,
31.33, 29.82, 29.57, 26.06, 22.87, 14.19 ppm; IR (KBr): n˜ =2962, 2876,
1694, 1595, 1474, 1384, 1260, 1093, 1017, 798, 623, 527 cmꢁ1; UV/Vis
(CH2Cl2): lmax (e)=254 (72500), 330 (41500), 405 (53500 sh), 425
(234500), 513 (6500), 551 (13500), 591 nm (7000 molꢁ1 cm3 dmꢁ1); MS
(ESI): m/z (%): 2501 (100) [M+]; elemental analysis (%) calcd for
10.0 Hz;
H
pyrrolidine), 5.07 (s, 1H; Hpyrrolidine), 4.13 (d, 1H, 2J(H,H)=
10.0 Hz; Hpyrrolidine), 4.03 (m, 4H; CH2O), 3.28 (m, 1H; CH2N), 2.58 (m,
1H; CH2N), 1.86 (m, 6H; CH2), 1.54–1.26 (m, 22H; CH2), 0.91 ppm (m,
9H; CH3); 13C NMR (50 MHz, CDCl3, 258C, TMS): d=151.17, 151.10,
147.32, 146.48, 146.32, 146.26, 146.22, 146.15, 146.10, 145.95, 145.92,
145.79, 145.55, 145.50, 145.34, 145.32, 145.27, 145.24, 145.16, 144.73,
144.65, 144.40, 143.16, 142.99, 142.68, 142.58, 142.54, 142.34, 142.27,
142.16, 142.13, 142.08, 142.03, 141.94, 141.89, 141.67, 141.52, 140.18,
140.13, 139.88, 139.55, 138.09, 137.97, 135.77, 135.70, 129.82, 128.86,
128.62, 128.32, 127.40, 127.06, 126.79, 126.73, 126.52, 123.91, 123.53,
110.78, 110.64, 82.48, 69.61, 69.57, 68.91, 53.24, 31.94, 31.62, 29.65, 29.47,
29.34, 27.58, 25.93, 22.72, 22.65, 22.63, 14.16, 14.06, 14.01 ppm; IR (KBr):
n˜ =2920, 2850, 1595, 1508, 1491, 1460, 1419, 1257, 1188, 1016, 960,
527 cmꢁ1; UV/Vis (CH2Cl2): lmax (e)=246 (115400), 255 (123600), 328
(64600), 394 nm (54400 molꢁ1 cm3 dmꢁ1); MS (ESI): m/z (%): 1356 (100)
[M+].
C
183H135N5O2Zn·CH3OH (2533.5): C 87.23, H 5.53, N 2.76; found: C
87.26, H 5.61, N 2.71.
15: Potassium tert-butoxide (168 mg; 1.5 mmol) was added portionwise to
a solution of 6 (1.05 g; 2 mmol) in dry THF (130 mL) at room tempera-
ture. The reaction was stirred for 20 min, and then a solution of benzalde-
hyde (106 mg, 1.0 mmol) in dry THF (35 mL) was added dropwise. After
2 h, methanol (5 mL) was added to the reaction mixture and the solvent
was evaporated. The resulting solid was purified by flash chromatography
(silica gel, CH2Cl2, CH2Cl2/MeOH (98/2)) to obtain 265 mg (53%) of 15
as a pale yellow oil.
18: Yield 49%; 1H NMR (200 MHz, CDCl3, 258C, TMS): d=7.80 (m,
2H; HAr), 7.64 (d, 2H, 3J(H,H)=8.6 Hz; HAr), 7.58 (d, 2H, 3J(H,H)=
8.6 Hz; HAr), 7.56 (d, 2H, 3J(H,H)=8.6 Hz; HAr), 7.53 (m, 4H), 7.52 (d,
2H, 3J(H,H)=16.3 Hz; Holef), 7.48 (m, 4H; HAr), 7.22 (d, 2H, 3J(H,H)=
16.3 Hz; Holef), 7.14 (d, 2H, 3J(H,H)=16.3 Hz; Holef), 7.12 (s, 2H; HAr),
3
2
7.09 (d, 2H, J(H,H)=16.3 Hz; Holef), 5.10 (d, 1H, J(H,H)=9.6 Hz; Hpyr-
rolidine), 5.06 (s, 1H; Hpyrrolidine), 4.11 (d, 1H, 2J(H,H)=9.6 Hz; Hpyrrolidine),
4.06 (m, 4H; CH2O), 3.24 (m, 1H; CH2N), 2.57 (m, 1H; CH2N), 1.88 (m,
6H; CH2), 1.56 (m, 8H; CH2), 1.40–1.26 (m, 14H; CH2), 0.93 ppm (m,
9H; CH3); 13C NMR (75 MHz, CDCl3, 258C, TMS): d=156.60, 154.28,
153.58, 153.54, 151.21, 151.13, 147.28, 146.81, 146.49, 146.28, 146.23,
146.19, 146.14, 146.10, 146.07, 145.91, 145.75, 145.53, 145.47, 145.30,
145.24, 145.20, 145.11, 144.70, 144.60, 144.37, 143.13, 142.97, 142.66,
142.55, 142.33, 142.26, 142.08, 141.99, 141.90, 141.82, 141.65, 141.50,
140.15, 140.11, 139.86, 139.50, 138.45, 137.40, 137.36, 136.88, 136.84,
136.55, 136.42, 135.82, 135.69, 135.30, 132.47, 132.05, 129.82, 128.66,
128.48, 128.03, 127.28, 127.17, 126.93, 126.85, 126.79, 126.67, 126.29,
124.12, 123.40, 119.05, 110.61, 110.51, 110.43, 82.36, 69.57, 69.52, 68.97,
66.87, 53.17, 31.96, 31.63, 29.67, 29.46, 29.36, 28.36, 27.58, 25.96, 22.74,
22.65, 14.19, 14.05 ppm; IR (KBr): n˜ =2922, 2852, 2222, 1630, 1593, 1508,
1491, 1464, 1421, 1203, 1172, 1018, 960, 527 cmꢁ1; UV/Vis (CH2Cl2): lmax
1H NMR (200 MHz, CDCl3, 258C, TMS): d=7.54–7.49 (m, 2H; HAr),
7.39 (m, 1H; HAr), 7.35 (s, 1H; HAr), 7.34 (d, 1H, 3J(H,H)=16.4 Hz;
Holef), 7.08 (d, 1H, 3J(H,H)=16.4 Hz; Holef), 7.07 (s, 1H; HAr), 6.92 (d,
3
1H, 3J(H,H)=2.8 Hz; HAr), 6.88 (d, 1H, J(H,H)=1.3 Hz; HAr), 3.97 (m,
4H; CH2O), 3.68 (d, 6H, 3J (H,P)=11.0 Hz; POCH3), 3.26 (d, 2H, 3J
(H,P)=21.0 Hz; PCH2), 1.80 (m, 4H; CH2), 1.53–1.25 (m, 12H; CH2),
0.90 ppm (m, 6H; CH3); 13C NMR (75 MHz, CDCl3, 258C, TMS): d=
150.93, 150.78, 137.94, 128.70, 128.66, 128.59, 127.34, 126.56, 126.46,
126.03, 123.66, 121.19, 120.37, 120.17, 69.52, 69.12, 52.79, 52.65, 31.61,
31.58, 29.38, 25.79, 22.61, 13.90 ppm; IR (KBr): n˜ =2950, 2935, 2856,
1506, 1475, 1421, 1269, 1213, 1058, 1028, 871, 754 cmꢁ1; UV/Vis (CH2Cl2)
lmax (e): 229 (6700), 295 (12900), 342 nm (9300 molꢁ1 cm3 dmꢁ1); MS (EI):
m/z (%): 522 (29) [M+], 418 (35) [M+ꢁC6H13], 393 (3), 334 (89) [M+
ꢁC6H13], 302 (17), 223 (100), 91 (14), 86 (23).
1278
ꢅ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 1267 – 1280