Supporting Information
Investigation of Catalyst-Transfer Condensation Polymerization for Synthesis of
Poly(p-phenylenevinylene)
MasatakaNojima, Yoshihiro Ohta, TsutomuYokozawa
Department of Material and Life Chemistry, Kanagawa University 3-27-1 Rokkakubashi,
Kanagawa-ku, Yokohama 221-8686, Japan
1
70
Yield of product (%)
60
50
40
30
20
10
0
0
20
40
60
80
100
120
Reaction time (min)
FIGURE S1
Yield of coupling product (4-methyl-1,1’-biphenyl) as a function of time
in the reaction of equimolar phenylmagnesium bromide and 4-bromotoluene in the
presence of 5 mol% of Ni(dppp)Cl2 (dashed line) and 5 mol% of Ni(dppp)Cl2 and
(1E,3E)-1,4-diphenylbuta-1,3-diene (solid line) in THF at rt.
2
= Br/H
= Br/Br
= I/Br
1900
2000
2100
2200
2300
2400
Mass / Charge
FIGURE S2
MALDI-TOF mass spectra of products obtained by the polymerization of
2 with 5.0 mol% of Ni(dppp)Cl2 in Et2O([2]0 = 0.1 M) at room temperature for 24 h (Mn
= 1860, Mw/Mn = 1.56).
(b)
2000
FIGURE S3
3000
Mass / Charge
4000
2000
2400
2600
2765.64 (Pinacol/I)
2639.76 (Pinacol/H)
2685.71 (B(OH)2/I)
2589.40 (Ph/H)
2407.01 (Pinacol/I)
2715.88 (Ph/I)
2356.98 (Ph/I)
2200
2326.78 (B(OH)2/I)
2231.19 (Ph/H)
2280.74 (Pinacol/H)
2045.74 (Pinacol/I)
1968.49 (B(OH)2/I)
1921.79 (Pinacol/H)
1872.31 (Ph/H)
1998.25 (Ph/I)
(a)
2800
MALDI-TOF mass spectra of products obtained by the polymerization of
3 in the presence of CsF/18-crown-6 and 5.0 mol% of 6 at 60 oC in THF and water ([3]0 =
3
8.33 x 10-3 M) for 24 h (Mn = 2320, Mw/Mn = 3.97);(a) whole spectrum, (b) magnification
between m/z = 2000-2800.
(b)
(a)
= Ph/Br
= B(OH)2/Br
= Pin/Br
= Ph/H
800
1200 1400 1600
Mass / Charge
1000
1800
5 min
3000
2000
(ｃ)
30 min min
4000
5000 6000 7000
Mass / Charge
8000
9000
8000
9000
(ｄ)
= Ph/H
800
1000
FIGURE S4
1200 1400 1600
Mass / Charge
1800
2000
3000
4000
5000 6000 7000
Mass / Charge
MALDI-TOF mass spectra of products obtained by the polymerization of
4 in the presence of KOH/18-crown-6 and 5.0 mol% of 6 in THF ([4]0 = 2.50 x 10-2
M)and water at -20 oC for 5 min (Mn = 4740, Mw/Mn = 2.16);(a) magnification between
m/z = 800-2000, (b) whole spectrum, and 30 min (Mn = 9450, Mw/Mn = 2.59);(c)
magnification, (d) whole spectrum.
4
(a)
(b)
= tolyl/H
= tolyl/tolyl
2000
3000
FIGURE S5
4000
5000
Mass / Charge
6000
7000
2150
2500
2250
2300
2350
2400
2450
Mass / Charge
2500
2550
MALDI-TOF mass spectra of PPV obtained by the polymerization of 5 in
the presence of KOH/18-crown-6 and 5.0 mol% of 7 in THF ([5]0 = 8.33 x 10-3 M) and
water at room temperature for144 h (Mn = 9980, Mw/Mn = 3.92); (a) whole spectrum, (b)
magnification between m/z = 2150-2550.
Model reaction of (E)-(2-bromovinyl)benzene and Pd(PtBu3)2.
All glass apparatus was dried prior to use. Addition of reagents into a reaction flask and
withdrawal of a small aliquot of the reaction mixture for analysis were carried out via a
syringe from a three-way stopcock under a stream of nitrogen. A round-bottomed flask
equipped with a three-way stopcock was heated under reduced pressure, and then cooled
to room temperature under an argon atmosphere. Pd(PtBu3)2 (25.7 mg, 0.05 mmol) was
placed in the flask, and the atmosphere in the flask was replaced with argon. A solution
of (E)-(2-bromovinyl)benzene (9.4 mg, 0.05 mmol) and naphthalene (6.6 mg, 0.05 mmol)
as an internal standard in dry THF (6.0 mL) was added to the flask via a syringe, and the
mixture was degassed with argon. The reaction mixture was stirred at room
5
temperaturefor 24 h, then reaction mixture was sampled. GC analysis of the sample
showed that(1E,3E)-1,4-diphenylbuta-1,3-diene was formed in 23% yield.
6