ARTICLE
Yield: 398 mg (74%). Mn ¼ 26,760 g/mol, Mw/Mn ¼ 1.87.
FTIR (ATR, cmꢁ1): 1763 (C¼¼OOC6F5), 1726 (C¼¼OOCH3), 1521
(s, CAF). 1H NMR (300 MHz, CDCl3, ppm): 3.85 (s, 3H, CH3),
6.69, 7.73 (br s, 10H, HC¼¼C, Ar). 19F NMR (400 MHz, CDCl3,
ppm): ꢁ152.75 (s, 2F), ꢁ157.65 (s, 1F), ꢁ162.14 (s, 2F).
solution of the polymer (1eq.) in chloroform was added first
NEt3 (1.05eq. related to the monomer units) then the corre-
sponding amine (1.10eq. related to the monomer units). The
mixture was stirred for the indicated time at the indicated
temperature. The organic layer was washed with water and
the resulting polymers were purified by precipitation into a
large amount of cyclohexane (P4_N1-3) or n-hexane (P4_N4-
6, P1/4_N1, P2/4c_N1), centrifuged and dried under
vacuum.
Poly(methyl 4-ethynylbenzoate-co-pentafluorophenyl
4-ethynylbenzoate) (P2/4d)
According to the general procedure the copolymerization of
M2 (88 mg, 0.5mol) with M4 (406 mg, 1.3 mmol) was con-
ducted using WCl6 (15 mg, 38 lmol) and SnPh4 (19 mg, 44
lmol) in toluene (3 mL) to give P2/4d as orange powder.
Poly(N-hexyl 4-ethynylbenzamide) (P4_N1)
According to the general procedure of the polymer analogous
reaction P4 (33 mg, 103 lmol), NEt3 (0.03 mL, 216 lmol)
and hexylamine (0.02 mL, 152 lmol) in chloroform (3 mL)
were stirred for 12 h at room temperature to yield P4_N1 as
an orange powder.
Yield: 376 mg (76%). Mn ¼ 20,030 g/mol, Mw/Mn ¼ 1.35.
FTIR (ATR, cmꢁ1): 1763 (C¼¼OOC6F5), 1725 (C¼¼OOCH3),
1
1519 (s, CAF). H NMR (300 MHz, CDCl3, ppm): 3.77 (s, 1H,
CH3), 6.63, 7.73 (br s, 10H, HC¼¼C, Ar).
Yield: 23 mg (95%). Mn ¼ 6240 g/mol, Mw/Mn ¼ 1.39. FTIR
(ATR, cmꢁ1): 3293 (NAH), 2955 and 2927 and 2856 (CH3,
CH2), 1637and 1541 (C¼¼ONH). 1H NMR (300 MHz, CDCl3,
ppm): 0.86 (s, 3H, CH3), 1.28 (s, 6H, CH2), 1.60 (s, 2H, CH2),
3.34 (s, 2H, CH2NH), 7.11 (br s, 5H, HC¼¼C, Ar).
Poly(methyl 4-ethynylbenzoate-co-pentafluorophenyl
4-ethynylbenzoate) (P2/4e)
According to the general procedure the copolymerization of
M2 (31 mg, 0.2mol) with M4 (524 mg, 1.7 mmol) was con-
ducted using WCl6 (15 mg, 38 lmol) and SnPh4 (16 mg, 37
lmol) in toluene (3 mL) to give P2/4e as orange powder.
Poly(phenylacetylene-co-N-hexyl 4-ethynylbenzamide)
(P1/4_N1)
Yield: 398 mg (72%). Mn ¼ 12,790 g/mol, Mw/Mn ¼ 1.39.
FTIR (ATR, cmꢁ1): 1763 (C¼¼OOC6F5), 1727 (C¼¼OOCH3),
1519 (s, CAF). 1H NMR (300 MHz, CDCl3, ppm): 3.72 (s,
0.5H, CH3), 6.62, 7.80 (br s, 10H, HC¼¼C, Ar).
According to the general procedure of the polymer analogous
reaction P1/4 (45 mg, 144 lmol), NEt3 (0.03 mL, 216 lmol)
and hexylamine (0.02 mL, 152 lmol) in chloroform (3 mL)
were stirred for 12 h at room temperature to yield P1/4_N1
as an orange powder.
Fractionated Precipitation of Poly(phenylacetylene) (P1)
P1 (70 mg, 5.7 lmol) was dissolved in 1.5 mL THF. Under
stirring MeOH was added until polymer began to precipitate.
The precipitated polymer fraction was separated from the
polymer solution by centrifugation. Precipitation was then
continued by further addition of MeOH (ꢃ2 mL) and the
process was continued for three times. The rest of the solu-
tion was finally evaporated to dryness. All fractions were
dried under vacuum to yield P1a, P1b, P1c, P1d and P1e as
orange powders. P1a: yield 35 mg, Mn ¼ 14,700 g/mol, Mw/
Yield: 26 mg (91%). Mn ¼ 19,300 g/mol, Mw/Mn ¼ 1.50
FTIR (ATR, cmꢁ1) ¼ 3355 (NAH), 2956 and 2926 and 2858
(CH3, CH2), 1637 and 1541 (C¼¼ONH). 1H NMR (300 MHz,
CD2Cl2, ppm): 0.85 (s, 3H, CH3), 1.26 (s, 6H, CH2), 1.56 (s,
2H, CH2), 3.35 (s, 2H, CH2NH), 7.03 (br s, 11H, HC¼¼C, Ar).
Poly(methyl 4-ethynylbenzoate-co-N-hexyl
4-ethynylbenzamide) (P2/4c_N1)
According to the general procedure of the polymer analogous
reaction P2/4c (41 mg, 131 lmol), NEt3 (0.03 mL, 216
lmol) and hexylamine (0.02 mL, 152 lmol) in chloroform (3
mL) were stirred for 12 h at room temperature to yield P2/
4c_N1 as an orange powder.
Mn ¼ 1.23. P1b: yield 9 mg, Mn ¼ 6800 g/mol, Mw/Mn
¼
1.18. P1c: yield 3 mg, Mn ¼ 3800 g/mol, Mw/Mn ¼ 1.15.
P1d: yield 3 mg, Mn ¼ 2400 g/mol, Mw/Mn ¼ 1.11. P1a:
yield 8 mg, Mn ¼ 600 g/mol, Mw/Mn ¼ 1.8.
Yield: 24 mg (88%). Mn ¼ 14,440 g/mol, Mw/Mn ¼ 1.40.
FTIR (ATR, cmꢁ1) ¼ 3328 (NAH), 2952 and 2931 and 2858
Fractionated Precipitation of Poly(pentafluorophenyl
4-ethynylbenzoate) (P4)
1
(CH3, CH2), 1723 (C¼¼O), 1640 and 1540 (C¼¼ONH). H NMR
P4 (50 mg, 4.7 lmol) was dissolved in 1.0 mL THF and the
fractionated precipitation was induced by addition of MeOH
following the procedure above. All fractions were dried
under vacuum to yield P4a, P4b, P4c, P4d and P4e as or-
ange powders. P4a: yield 18 mg, Mn ¼ 13,000 g/mol, Mw/
Mn ¼ 1.29. P4b: yield 13 mg, Mn ¼ 10,100 g/mol, Mw/Mn ¼
1.13. P4c: yield 4 mg, Mn ¼ 7100 g/mol, Mw/Mn ¼ 1.09.
P4d: yield 3 mg, Mn ¼ 4600 g/mol, Mw/Mn ¼ 1.14. P4a:
yield 4 mg, Mn ¼ 3100 g/mol, Mw/Mn ¼ 1.13.
(300 MHz, CD2Cl2, ppm): 0.88 (s, 3H, CH3), 1.30 (s, 6H, CH2),
1.58 (s, 2H, CH2), 3.39 (s, 2H, CH2NH), 3.85 (s, 3H, COOCH3),
7.59 (br s, 10H, HC¼¼C, Ar).
Poly(N-isopropyl 4-ethynylbenzamide) (P4_N2)
According to the general procedure of the polymer analogous
reaction P4 (36 mg, 115 lmol), NEt3 (0.03 mL, 216 lmol)
and isopropylamine (0.02 mL, 233 lmol) in chloroform (3
mL) were stirred for 12 h at room temperature to yield
P4_N2 as an orange powder.
Polymer Analogous Reaction
General Procedure
Polymers and copolymers of M4 were converted with differ-
ent amines according to the same general procedure: To a
Yield: 21 mg (96%). Mn ¼ 6170 g/mol, Mw/Mn ¼ 1.35. FTIR
(ATR, cmꢁ1): 3299 (NAH), 2972 and 2934 and 2874 (CH3,
CH), 1636 and 1536 (C¼¼ONH). 1H NMR (300 MHz, CDCl3,
POLY(PHENYLACETYLENES) FEATURING ACTIVATED ESTER SIDE GROUPS, PAULY AND THEATO
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