Synthesis of End-Functionalized Single-Oligomer OPVs
(s, 1H). 13C NMR (CDCl3, 62.9 MHz) δ: 14.1, 24.4, 24.6, 55.3,
114.2, 125.5, 126.2, 126.6, 126.9, 127.8, 127.9, 128.2, 129.6,
130.2, 130.3, 134.2, 135.2, 136.0, 136.7, 137.1, 138.4, 138.8,
144.0, 159.4, 191.5. Anal. Calcd for C30H32O2: C, 84.87; H, 7.60.
Found: C, 84.9; H, 7.8.
containing a solution of sodium carbonate in water. The orange
product was filtered off and washed with water and ethanol.
Me2N-OP V 10. Yield: 85%. Mp: 195-8 °C. UV-vis [chlo-
1
roform, λmax (ꢀ)]: 414 (82 100). H NMR (CDCl3, 250.1 MHz)
δ: 1.04 (t, 12H, J ) 7 Hz), 1.69 (m, 8H), 2.78 (t, 6H, J ) 8
Hz), 3.00 (s, 3H), 6.74 (d, 2H, J ) 8 Hz), 6.9-7.6 (m, 21H),
7.67 (s, 1H), 10.26 (s, 1H). MS (MALDI-TOF): m/z 725.56,
calcd for C53H59NO 725.4597.
Me2N-OP V 11. Yield: 89%. Mp > 250 °C. UV-vis [chloro-
form, λmax (ꢀ)]: 421 (138 400). 1H NMR (CDCl3, 250.1 MHz) δ:
1.05 (t, 18H, J ) 8 Hz), 1.69 (m, 12H), 2.78 (t,10H, J ) 7 Hz),
3.00 (s + t, 3H + 2H), 6.73 (d, 2H, J ) 8 Hz), 6.9-7.6 (m,
31H), 7.66 (s, 1H), 10.26 (s, 1H). MS (MALDI-TOF): m/z
1013.86, calcd for C75H83NO 1013.6475.
MeO-OP V Ad d u ct w ith Ma lod in itr ile (12). MeO-OPV 6
(500 mg, 0.5 mmol) was dissolved in THF (25 mL) together
with an excess of malodinitrile (300 mg). Piperidine (1 mL)
and ethanol (5 mL) were added, and the reaction mixture was
heated to reflux for 1 h. The solvents were removed in a
vacuum, the residue was triturated with ethanol (50 mL), and
the solid product was filtered off and washed with more
ethanol and petroleum ether. Yield: 480 mg, 96%. Mp: 235
°C dec. 1H NMR (CDCl3, 250.1 MHz) δ: 1.01 (m, 18H), 1.67
(m,12H), 2.76 (m,12H), 3.84 (s, 6H), 6.92 (d, 2H, J ) 8 Hz),
7.0-7.5 (m, 32H), 8.03 (d, 2H, J ) 7 Hz). MS (MALDI-TOF):
m/z 1073.66, calcd for C78H79N3O 1073.6223.
Gen er a l P r oced u r e for th e P r ep a r a tion of th e OP Vs
5-8. Monomer 1 and an equal amount of aldehyde-terminated
OPV (4, 5, 6, or 7) was mixed in dry THF and purged with
argon. Then potassium tert-butoxide (2 equiv, excess) was
added, and the mixture was refluxed for 30 min to complete
the reaction. The cooled mixture was diluted with water and
acidified with hydrochloric acid. The precipitate was filtered
and washed with water and ethanol. The moist product was
then dissolved in THF, and concentrated hydrochloric acid was
added to hydrolyze the acetal at reflux for 30 min. The mixture
was diluted with an equal volume of water and the solvent
removed in a vacuum. The precipitated product was filtered
and washed thoroughly with water and ethanol.
MeO-OP V 5. Yield: 4.36 g, 6.11 mmol 69%. Mp: 185-9
°C. UV-vis [chloroform, λmax (ꢀ)]: 402 (84 400). 1H NMR
(CDCl3, 250.1 MHz) δ: 1.05 (t, 12H, J ) 8 Hz), 1.70 (p, 8H,
J ) 8 Hz), 2.78 (t, 6H, J ) 8 Hz), 3.03 (t, 2H, J ) 8 Hz), 3.84
(s, 3H), 6.9-7.7 (m, 22H), 10.26 (s, 1H). Anal. Calcd for
C
52H56O2: C, 87.60; H, 7.92. Found: C, 87.8; H, 8.1.
MeO-OP V 6. Yield: 5.52 g, 5.5 mmol, 96%. Mp: 230-2 °C.
UV-vis [chloroform, λmax (ꢀ)]: 408 (132 000). 1H NMR (CDCl3,
250.1 MHz) δ: 1.05 (t, 18H, J ) 8 Hz), 1.73 (m, 12H), 2.78 (t,
8H, J ) 8 Hz), 3.02 (t, 2H, J ) 8 Hz), 3.84 (s, 3H), 6.9-7.7 (m,
34H), 10.26 (s, 1H). Anal. Calcd for C74H80O2: C, 88.75; H,
8.05. Found: C, 88.6; H, 8.1.
Gen er a l P r oced u r e for th e OP Vs 13-16. MeO-OPV 6
was dissolved in THF (25 mL) together with diethyl ben-
zylphosphonate ester, diethyl 4-methoxybenzylphosphonate
ester, diethyl 4-nitrobenzylphosphonate ester, or diethyl
2,3,4,5,6-pentaflurobenzylphosphonate ester (500 mg, excess).
Potassium tert-butoxide (0.25 g, excess) was added, and the
mixture was heated to reflux for 30 min. The cooled mixture
was mixed with dilute hydrochloric acid and the THF removed
in a vacuum. The residue was filtered off and washed with
water (2 × 200 mL) and ethanol (2 × 100 mL). After drying,
the crude solid was taken up in chloroform and filtered through
a layer of silica. The solvent was again removed in a vacuum.
OP V 13. From 6 and diethyl benzylphosphonate ester.
MeO-OP V 7. Yield: 87%. Mp > 250 °C. UV-vis [chloro-
form, λmax (ꢀ)]: 416 (135 000). 1H NMR (CDCl3, 250.1 MHz) δ:
1.06 (t, 24H, J ) 8 Hz), 1.71 (m, 16H), 2.79 (t, 14H, J ) 7 Hz),
3.03 (t, 2H, J ) 8 Hz), 3.84 (s, 3H), 6.9-7.7 (m, 44H), 10.26 (s,
1H). Anal. Calcd for C96H104O2: C, 89.39; H, 8.13. Found: C,
89.0; H, 8.2.
MeO-OP V 8. Yield: 57%. Mp > 250 °C. UV-vis [chloro-
form, λmax (ꢀ)]: 420 (144 000). 1H NMR (o-C6D4Cl2, 250.1 MHz,
400 K) δ: 1.09 (t, 30H, J ) 8 Hz), 1.78 (m, 20H), 2.87 (broad,
18H), 3.03 (broad, 2H), 3.72 (s, 3H), 6.9-7.7 (m, 54H), 10.30
(s, 1H). Anal. Calcd for C118H128O2: C, 89.80; H, 8.17. Found:
C, 89.6; H, 8.4.
1
Yield: 88%. Mp: 247-9 °C. H NMR (CDCl3, 250.1 MHz) δ:
1.06 (t, 18H, J ) 8 Hz), 1.6-1.8 (m, 12H), 2.79 (t, 12H, J ) 7
Hz), 3.84 (s, 3H), 6.92 (d, 2H, J ) 7 Hz), 7.0-7.6 (m, 39H).
MS (MALDI-TOF): m/z 1074.69, calcd for C81H86O 1074.6679.
OP V 14. From 6 and diethyl 4-methoxybenzylphosphonate
ester. Yield: 70%. Mp: 246-50 °C. 1H NMR (CDCl3, 250.1
MHz) δ: 1.05 (t,18H,J ) 7 Hz), 1.74 (m, 12H), 2.79 (t, 12H,
J ) 7 Hz), 3.85 (s, 3H), 3.86 (s, 3H), 6.9-7.6 (m, 40H). MS
(MALDI-TOF): m/z 1104.63, calcd for C82H88O2 1104.6784.
OP V 15. From 6 and diethyl 4-nitrobenzylphosphonate
ester. Yield: 66%. Mp > 250 °C. 1H NMR (CDCl3, 250.1 MHz)
δ: 1.05 (t, 18H, J ) 8 Hz), 1.73 (m, 12H), 2.78 (t, 12H, J ) 7
Hz), 3.84 (s, 3H), 6.92 (d, 2H, J ) 9 Hz), 7.0-7.6 (m, 34H),
7.65 (d, 2H, J ) 9 Hz), 8.25 (d, 2H, J ) 9 Hz). MS (MALDI-
TOF): m/z 1119.78, calcd for C81H85NO3 1119.6529.
Me2N-OP V 9. Monomer 1 (3.0 g, 5.7 mmol) and N,N-
dimethylbenzaldehyde (1.0 g, 6.7 mmol) were dissolved in THF
(100 mL). Then potassium tert-butoxide (2 equiv, excess) was
added, and the mixture was refluxed for 30 min to complete
the reaction. The cooled mixture was hydrolyzed with 25 mL
of concentrated hydrochloric acid for 30 min at ambient
temperature. The mixture was cautiously neutralized by
pouring it into a beaker containing a solution of sodium
carbonate in water. The orange product was filtered off and
washed with water and ethanol. Yield: 2.35 g, 94%. Mp:
158-9 °C. UV-vis [chloroform, λmax (ꢀ)]: 407 (46 200). 1H NMR
(CDCl3, 250.1 MHz) δ: 1.00 (t, 3H, J ) 7 Hz), 1.03 (t, 3H, J )
7 Hz), 1.61-1.77 (m, 4H), 2.78 (t, 2H, J ) 7 Hz), 3.01 (s + t,
8H), 6.72 (d, 2H, J ) 8 Hz), 6.93 (d, 1H, J ) 16 Hz), 7.11 (d,
1H, J ) 16 Hz), 7.13 (d, 1H, J ) 16 Hz), 7.34 (d, 1H, J ) 16
Hz), 7.44 (d, 2H, J ) 8 Hz), 7.51 (s + s, 4 + 1H), 7.65 (s, 1H),
10.25 (s, 1H). 13C NMR (CDCl3, 62.9 MHz) δ: 14.0, 23.9, 25.5,
34.2, 34.9, 40.4, 112.5, 123.8, 124.4, 125.7, 126.4, 126.8, 127.7,
127.9, 129.3, 132.4, 132.5, 132.7, 135.5, 138.4, 141.4, 143.1,
150.2. Anal. Calcd for C31H35NO: C, 85.08; H, 8.06; N, 3.20.
Found: C, 85.1; H, 8.2; N, 3.1.
OP V 16. From 6 and diethyl 2,3,4,5,6-pentaflurobenzylphos-
1
phonate ester. Yield: 94%. Mp: 245-8 °C. H NMR (CDCl3,
250.1 MHz) δ: 1.05 (t, 18H, J ) 7 Hz), 1.70 (m, 12H), 2.78 (t,
12H, J ) 7 Hz), 3.85 (s, 3H), 6.92 (d, 2H, J ) 8 Hz), 7.0-7.6
(m, 34H). MS (MALDI-TOF): m/z 1164.67, calcd for C81H81F5O
1164.6207.
Cya n in e Der iva tive of OP V 6 (17). Compound 6 (1.0
mmol) was dissolved in hot dioxane (100 mL) together with
acetal-protected ethyl phosphonylmethylbenzaldehyde (1 g, 2.9
mmol), and then potassium tert-butoxide (1.1 g, 10 mmol) was
added and the mixture heated to reflux for 30 min. The cooled
reaction mixture was poured into dilute hydrochloric acid and
filtered. The filter cake was redissolved in dioxane and added
to concentrated hydrochloric acid and stirred for 30 min to
hydrolyze the acetal. The solvent was removed in a vacuum
and the residue filtered, washed with ethanol, and dried.
The extended oligomer was dissolved in dioxane (100 mL)
at reflux. An equal amount of 1,2-dimethylbenzothiazolium
Gen er a l P r oced u r e for th e P r ep a r a tion of th e OP Vs
10 a n d 11. Monomer 1 and an equal amount of aldehyde-
terminated OPV (9 or 10) were dissolved in THF (100 mL).
Then potassium tert-butoxide (2 equiv, excess) was added, and
the mixture was refluxed for 30 min to complete the reaction.
The cooled mixture was hydrolyzed with 25 mL of concentrated
hydrochloric acid for 30 min at ambient temperature. The
mixture was cautiously neutralized by pouring it into a beaker
J . Org. Chem, Vol. 69, No. 20, 2004 6695