Macromolecules, Vol. 37, No. 20, 2004
Conjugated Polyacetylenes 7445
2-(4-Eth yn yloxy-ph en yl)-3,4-fu ller opyr r olidin e (1a). Gly-
cine (75 mg, 1 mmol), 4-prop-2-ynyloxybenzaldehyde (400 mg,
2.5 mmol), and C60 (360 mg, 0.5 mmol) were dissolved in
chlorobenzene, and the mixture was refluxed for 6 h under
stirring. After cooling, the solvent was evaporated under
reduced pressure. The crude solid was purified on silica gel
column using toluene as the eluent (Rf ) 0.1), yielding a black
powder (178 mg, 40%). 1H NMR (400 MHz, CDCl3, TMS): δ )
7.73 (d, J ) 8.6 Hz, 2H), 7.03 (d, J ) 8.6 Hz, 2H), 5.76 (s, 1H),
5.09 (d, J ) 10.4 Hz, 1H), 4.87 (d, J ) 10.4 Hz, 1H), 4.70 (s,
2H), 3.26 (s, 1H), 2.51 (s, 1H). 13C NMR (600 MHz, C6D6): δ )
157.39, 155.96, 153.62, 153.44, 153.04, 146.65, 146.41, 146.06,
145.83, 145.78, 145.73, 145.63, 145.58, 145.42, 145.21, 145.04,
144.98, 144.87, 144.84, 144.80, 144.77, 144.71, 144.21, 144.04,
143.94, 143.90, 142.77, 142.62, 142.27, 142.16, 142.07, 141.92,
141.89, 141.73, 141.69, 141.63, 141.55, 141.49, 141.45, 141.24,
141.04, 139.69, 139.51, 139.25, 136.19, 135.79, 135.46, 128.87,
114.79, 77.99, 76.84, 76.11, 74.91, 60.75, 54.89. FT-IR (KBr):
ν ) 3295, 2914, 2809, 2121, 1609, 1560, 1428, 1221, 1028, 825,
527. MALDI-TOF MS: m/z 894 [M + H]+. Anal. Calcd for
C71H11NO: C, 95.41; H, 1.24; N, 1.57. Found: C, 94.94; H, 1.06;
N, 1.49.
washed with water and dried over anhydrous NaSO4. The
solvent was removed in vacuo. 1H NMR (400 MHz, CDCl3,
TMS): δ ) 9.06 (s, 4H), 9.05 (d, J ) 5.2 Hz, 2H), 9.00 (d, J )
4.7 Hz, 2H), 8.14 (d, J ) 8.5 Hz, 2H), 7.47 (s, 6H), 7.36 (d, J
) 8.5 Hz, 2H), 4.98 (s, 2H), 4.17 (s, 9H), 3.95 (s, 18H), 2.70 (s,
1H). 13C NMR (600 MHz, CDCl3): δ ) 157.36, 151.26, 150.64,
150.30, 150.25, 150.23, 138.31, 137.71, 136.00, 135.33, 132.16,
132.06, 132.02, 121.00, 120.88, 113.11, 112.82, 78.71, 75.88,
61.27, 56.38, 56.17. FT-IR (KBr): ν ) 3278, 2939, 2831, 2127,
1579, 1492, 1459, 1348, 1235, 1126, 1000, 799. MALDI-TOF
MS: m/z 1001 [M + H]+. Anal. Calcd for C56H48N4O10Zn: C,
67.10; H, 4.83; N, 5.59. Found: C, 66.73; H, 4.96; N, 5.84.
P olym er iza tion . Polymerization was carried out in a dry
glass ampule under a N2 atmosphere using [Rh(nbd)Cl]2 as
catalyst. A typical polymerization procedure is described below.
Monomer 1a (26.8 mg, 0.03 mmol) and monomer 5 (107.1
mg, 0.279 mmol) were placed in a dry ampule, which was then
evacuated on a vacuum line and flushed with dry nitrogen.
After this evacuation-flush procedure was repeated three
times, a three-way stopcock was attached to the ampule, and
dry chloroform (6.7 mL) and triethylamine (40 µL) were added
with a syringe. To this was added a solution of a rhodium
catalyst in chloroform (0.3 mL) at 30 °C. The concentrations
of the monomer and the rhodium catalyst were 4.3 and 0.86
N-Dod ecyl-2-(4-eth yn yloxy-p h en yl)-3,4-fu ller op yr r oli-
d in e (1b). Compound 1a (134 mg, 0.15 mmol) and dodecanal
(138 mg, 0.75 mmol) were mixed in dichloromethane (50 mL)
and then treated with sodium triacetoborohydride (159 mg,
0.75 mmol) and AcOH (35 µL). The mixture was stirred at
room temperature under a N2 atmosphere for 12 h until the
reactants were consumed as determined by TLC analysis. The
reaction mixture was quenched by adding aqueous saturated
NaHCO3 solution, and the product was extracted with dichlo-
romethane. The extract was dried over MgSO4, and the solvent
was evaporated. The crude product was purified on silica gel
using petroleum ether/toluene (10/1 (v/v), Rf ) 0.6); yield: 127
mM, respectively. After 24 h, the resulting polymer poly(1a 0.2
-
co-50.8) was precipitated into a large amount of methanol,
collected by centrifugation, washed with methanol, and dried
in vacuo at room temperature for 10 h.
Sp ectr oscop ic Da ta of th e P olym er s. Poly(1a 0.2-co-50.8):
1H NMR (400 MHz, CDCl3/C6D6CD3, TMS): δ ) 9.0-8.8 (broad
s), 8.2-7.9 (broad s), 7.6-7.3 (broad s), 5.5-5.3 (broad s,
-CHdC), 5.0-4.8 (broad s), 4.2-3.3 (broad d). FT-IR (KBr):
ν ) 2959.9, 2831.6, 1579.7, 1503.0, 1348.8, 1258.8, 1126.9,
1004.1, 801.2, 527.5. Poly(50.2-co-20.8): 1H NMR (400 MHz,
CDCl3, TMS): δ ) 9.1 (s), 8.2-8.0 (broad s), 7.5 (s), 7.1-6.8
(broad s), 5.3-4.9 (broad m), 4.7-4.3 (broad m), 4.2 (s), 4.0
(s), 3.0-2.8 (broad m), 2.0-1.9 (broad s), 1.6-1.3 (broad s).
FT-IR (KBr): ν ) 2976.1, 2934.6, 1715.1, 1507.6, 1237.3,
1167.0, 1002.0. Poly(1b): 1H NMR (400 MHz, CDCl3/CS2,
TMS): δ ) 7.7-7.5 (broad s, 2H), 6.9-6.5 (broad s, 2H), 5.3
(broad s, 1H, -CHdC), 5.2-5.0 (broad s, 2H), 4.8-4.6 (broad
s, 2H), 4.2-4.1 (broad s, 1H), 3.3-3.1 (broad s, 1H), 2.6-2.4
(broad s, 1H) 2.1-1.7 (broad m, 2H), 1.6-1.3 (m, 18H), 0.9 (t,
3H). FT-IR (KBr): ν ) 2920.6, 2849.4, 1607.6, 1507.1, 1175.1,
1109.9, 1015.5, 526.9. Poly(1a 0.1-co-20.9): FT-IR (KBr): ν )
2964.3, 1718.2, 1509.2, 1260.9, 1096.9, 1019.7, 802.9, 527.1.
1
mg, 80%. H NMR (400 MHz, CDCl3): δ ) 7.74 (bs, 2H), 7.02
(d, J ) 8.6 Hz, 2H), 5.09 (d, J ) 9.1 Hz, 1H), 5.02 (s, 1H), 4.69
(s, 2H), 4.12 (d, J ) 9.2 Hz, 1H), 3.20 (m, 1H), 2.52 (m, 1H),
2.17 (s, 1H), 1.86-1.90 (m, 2H), 1.67-1.29 (m, 18H), 0.89 (t, J
) 6.72 Hz, 3H). 13C NMR (600 MHz, CDCl3): δ ) 157.62,
156.72, 154.43, 153.71, 147.31, 146.81, 146.52, 146.31, 146.27,
146.22, 146.14, 146.11, 145.93, 145.76, 145.55, 145.48, 145.32,
145.28, 145.24, 145.21, 145.15, 144.74, 144.65, 144.41, 143.19,
143.03, 142.68, 142.56, 142.37, 142.30, 142.12, 142.01, 141.98,
141.83, 141.68, 141.52, 140.17, 140.13, 139.90, 139.51, 136.84,
136.59, 135.81, 135.74, 130.60, 130.40, 114.91, 82.04, 78.50,
75.63, 68.87, 66.87, 55.92, 53.12, 31.98, 29.78, 29.74, 29.58,
29.52, 29.43, 28.39, 27.60, 22.75, 14.19. FT-IR (KBr): 3301,
2921, 2850, 2126, 1609, 1508, 1428, 1219, 1030, 833, 527.
Resu lts a n d Discu ssion
MALDI-TOF MS: m/z 1062 (M + H)+. Anal. Calcd for C83H35
-
Scheme 1 illustrates the synthetic routes for the novel
monomers containing monosubstituted acetylene. 4-
[10,15,20-Tris(3,4,5-trimethoxyphenyl)porphyrin-5-yl]-
phenol was prepared by condensation of p-hydroxyben-
zaldehyde, 3,4,5-trimethoxybenzaldehyde, and pyrrole
(1:3:4, molar ratio) involving (C2H5)2O‚BF3 catalysis,
followed by oxidation with tetrachloro-p-benzoquinone
in CHCl3.10 In our strategy, 4-[10,15,20-tris(3,4,5-tri-
methoxyphenyl)porphyrin-5-yl]phenol was chosen for
two reasons. First, methoxy groups would undoubtedly
lead to polymers having a pronounced solubility. Second,
the electron-donor character of the tetrapyrrolic mac-
rocycle was enhanced by the presence of methoxy groups
in a para position on the peripheral phenyl rings.11
Compounds 2 and 4 were synthesized by alkylation of
4-[10,15,20-tris(3,4,5-trimethoxyphenyl)porphyrin-5-yl]-
phenol and N-(tert-butoxycarbonyl)-L-tyrosine with pro-
pargyl bromide in high yields, respectively. 2-(4-
Ethynyloxyphenyl)-3,4-fulleropyrrolidine (1a) was synthe-
sized from glycine and 4-prop-2-ynyloxybenzaldehyde,
based on the 1,3-dipolar cycloaddition of azomethine
ylides to C60.12a To improve the solubility of polymers,
we synthesized N-dodecyl-2-(4-ethynyloxyphenyl)-3,4-
fulleropyrrolidine (1b) from (1a ) by using a facile
NO: C, 93.87; H, 3.30; N, 1.32. Found: C, 93.19; H, 3.38; N,
1.03.
5-(4-P r op -2-yn ylo xy p h e n yl)-10,15,20-t r is(3,4,5-t r i-
m eth oxyp h en yl)p or p h yr in e (4). 4-[10,15,20-Tris(3,4,5-tri-
methoxyphenyl)porphyrin-5-yl]phenol (3) (364 mg, 0.4 mmol)
and K2CO3 (138 mg, 1 mmol) were suspended in acetone (50
mL), propargyl bromide (86 µL, 0.8 mmol, 80 wt % solution in
toluene) was slowly added, and the reaction mixture was
stirred and maintained reflux for 10 h. After cooling to room
temperature, the mixture was concentrated. Water (100 mL)
and dichloromethane (100 mL) were added, the layers were
dried (MgSO4), and the solvent was removed under reduced
pressure. The residue was purified on silica gel column using
chloroform as eluent (Rf ) 0.2) (330.5 mg, 88%). 1H NMR (400
MHz, CDCl3, TMS): δ ) 8.96 (s, 4H), 8.95 (d, J ) 5.1 Hz, 2H),
8.96 (d, J ) 4.7 Hz, 2H), 8.15 (d, J ) 8.6 Hz, 2H), 7.47 (s, 6H),
7.38 (d, J ) 8.6 Hz, 2H), 4.99 (s, 2H), 4.18 (s, 9H), 3.97 (s,
18H), 2.71 (s, 1H), -2.78 (s, 2H). FT-IR (KBr): ν ) 3316, 2928,
2853, 1581, 1503, 1464, 1409, 1357, 1235, 1127, 803. MALDI-
TOF MS: m/z 939 [M + H]+. Anal. Calcd for C56H50N4O10: C,
71.63; H, 5.37; N, 5.97. Found: C, 71.34; H, 5.23; N, 5.68.
5-(4-P r op -2-yn ylo xy p h e n yl)-10,15,20-t r is(3,4,5-t r i-
m eth oxyp h en yl)-21H,23H-p or p h yr in e Zin c (5). Saturated
zinc acetate-methanol solution (3 mL) was added to a solution
of compound 4 (198 mg, 0.2 mmol) in chloroform (30 mL). The
mixture was stirred at room temperature for 3 h and then was