SUPPLEMENTARY INFORMATION
1.
13
C NMR Resonances of Select Compounds
All
13
C NMR spectra were obtained using a Varian
Mercury 300 spectrometer (corresponding to
74.5 MHz for
13
C), recorded in CDCl
3
, and referenced to tetramethyls
ilane. The authors referred to
information compiled in the Spectral Database
for Organic Compounds (available online at
http://riodb01.ibase.aist.go.jp/s
dbs/cgi-bin/direct_fra
me_top.cgi) in the process of assigning
13
C
NMR resonances.
2-Chloroethyl-
p
-toluenesulfonate (1).
13
C NMR:
δ
= 145.30 (e), 132.44 (b), 130.00 and 127.97 (c
and d), 69.02 (f), 40.83 (g), 21.67 (a).
S
O
O
O
Cl
ab
cd
e
f
g
4'-(2-(Benzoylthio)ethoxy)[1,1’-biphenyl]-4-carbonitrile (3).
13
C NMR:
δ
= 191.40 (e), 159.00
(j), 145.11 (n), 136.64 (d), 133.69 (a), 132.57 (p), 131.89 (m), 128.70 and 127.30 (b and c), 128.43
(l), 127.13 (o), 119.09 (r), 115.21 (k),
110.14 (q), 66.70 (g), 28.13 (f).
rq
po
n
O
S
O
N
m
l
k
j
g
f
e
d
c
b
a
4'-(2-(2-(Benzoylthio)ethoxy)ethoxy) [1,1
’-biphenyl]-4-carbonitrile (6).
13
C NMR:
δ
= 191.54
(e), 159.35 (j), 145.12 (n), 136.82 (d), 133.48 (a), 132.54 (p), 131.63 (m), 128.61 and 127.23 (b and
c), 128.30 (l), 127.07 (o), 119.10 (r), 115.22 (k), 110.06 (q), 70.05 and 69.38 (h and i), 67.50 (g),
28.65 (f).
rq
po
n
O
S
O
N
m
l
k
j
g
f
e
d
c
b
a
O
h
i
Thiobenzoic acid S-[2-(9-carbazolyl)ethyl] ester (8).
13
C NMR:
δ
= 191.73 (e), 140.07 (h),
136.71 (d), 133.73 (a), 128.74 and 127.35 (b and c), 125.9
1 (j), 122.98 (m), 120.40 (l), 119.26 (k),
108.74 (i), 42.42 (g), 27.28 (f).
N
S
O
g
f
e
d
c
b
a
h
i
j
k
l
m
3,5-Dinitrobenzoic acid 3-(ace
tylthio)propyl ester (10).
13
C NMR:
δ
= 195.36 (b), 162.49 (f),
148.67 (i), 133.81 (g), 129.52 (h), 122.47 (j), 65
.21 (e), 30.64 (a), 28.68 and 25.50 (c and d).
S
O
c
ba
O
O
O
2
N
NO
2
d
e
f
g
h
i
j
4-Hydroxybenzoic acid 2-(benzo
ylthio)ethyl ester (12).
13
C NMR:
δ
= 191.42 (e), 166.27 (h),
160.24 (l), 136.65 (d), 133.68 (a),
132.09 (j), 128.70 and 127.32 (b
and c), 122.13 (i), 115.28 (k),
63.11 (g), 27.86 (f).
O
S
O
g
f
e
d
c
b
a
O
HO
h
i
j
k
l
Thiobenzoic acid S-[3-pyr
idinylmethyl] ester (13).
13
C NMR:
δ
= 190.74 (e), 150.14 (h), 148.62
(i), 136.48 and 136.42 (d and k), 133.70 and 133.65 (a and g), 128.71 and 127.31 (b and c), 123.46
(j), 30.38 (f).
S
O
g
f
e
d
c
b
a
N
h
i
j
k
2.
1
H NMR Spectra of Select Functionalized Polymers
All spectra were taken in CDCl
3
, resulting in a solvent peak in each case at
δ
= 7.24 ppm. Peaks
near 1.6 ppm correspond to wa
ter, and visible peaks at
δ
= 6.97, 2.27, and 1.43 ppm belong to BHT.
c
d,e
a
b
a
b
c
d,e
c
d,e
a
b
a
b
c
d,e
Figure A.1.
1
H NMR trace of unfunctionalized
prepolymer 92 kg/mol 1,2-PB.
1
S
S
OH
OH
1
2,3
45,6
7
8
7
8
2,3
4,5,6
main-chain and
cyclic protons
1
S
S
OH
OH
1
2,3
45,6
7
8
7
8
2,3
4,5,6
main-chain and
cyclic protons
Figure A.2.
1
H NMR trace of functionalized 1,2-PB polymer 92kPB-
OH (experimental c
onditions are given in Table 2).
2,3
1
main-chain and
cyclic protons
S
S
O
O
1
2,3
45,6
7
8
O
O
9
10
O
2
N
NO
2
O
2
N
NO
2
4,5,6
8
10 9
7
2,3
1
main-chain and
cyclic protons
S
S
O
O
1
2,3
45,6
7
8
O
O
9
10
O
2
N
NO
2
O
2
N
NO
2
4,5,6
8
10 9
7
Figure A.3.
1
H NMR trace of functionalized 1,2 PB polymer 92kPB-DNB (experimental conditions are given in Table 2).
S
S
1
2,3
45,6
7
8
9
10
11
N
N
12
main-chain and
cyclic protons
2,3
4,5,6
1
7
8
11
12
9,10
S
S
1
2,3
45,6
7
8
9
10
11
N
N
12
main-chain and
cyclic protons
2,3
4,5,6
1
7
8
11
12
9,10
Figure A.4.
1
H NMR trace of functionalized 1,2 PB polymer 820kPB8 (experimental conditions are given in Table 1).
4,5,6
main-chain and
cyclic protons
2,3
1
7
8
12
10
9
S
S
O
O
1
2,3
45,6
7
8
CN
CN
11
12
13
14
O
O
9
10
13,14
11
4,5,6
main-chain and
cyclic protons
2,3
1
7
8
12
10
9
S
S
O
O
1
2,3
45,6
7
8
CN
CN
11
12
13
14
O
O
9
10
13,14
11
Figure A.5.
1
H NMR trace of functionalized 1,2 PB polymer 92kPB6 (experimental conditions are given in Table 1).
4,5,6
main-chain and
cyclic protons
2,3
1
7
8
910
S
S
O
O
1
2,3
45,6
7
8
O
O
OH
OH
9
10
4,5,6
main-chain and
cyclic protons
2,3
1
7
8
910
S
S
O
O
1
2,3
45,6
7
8
O
O
OH
OH
9
10
Figure A.6.
1
H NMR trace of functionalized 1,2 PB polymer 820kPB12 (experimental conditions are given in Table 1).
3. 1,2-Polybutadiene Functionalization using 9-[2
-[(Triphenylmethyl)thio]e
thyl]carbazole (14)
Synthesis of 9-(2-Chloroethyl)carbazole (7).
The procedure was outlined in the description of the
preparation of
8
.
1
H NMR (300 MHz, CDCl
3
):
δ
= 8.09 (d, 2 carbazole H,
J
= 7.8 Hz), 7.50-7.37
(m, 4 carbazole H), 7.29-7.20 (m, 2 carbazole H), 4.60 (t, NC
H
2
,
J
= 7.2 Hz), 3.83 (t, C
H
2
Cl,
J
=7.2
Hz).
13
C NMR (300 MHz, CDCl
3
):
δ
= 140.07, 125.91, 123.07, 120.50, 119.50, 108.43, 44.64,
40.99.
Synthesis of 9-[2-[(Triphenylmethyl)thio]ethyl]carbazole (14).
Potassium carbonate (4.4 g, 32
mmol), triphenylmethyl mercaptan (Alfa Aesar, 98%, 3.1 g, 11 mmol), and 9-(2-
chloroethyl)carbazole (2.1 g, 9.1 mmol)
were stirred at r.t. in 50 mL
DMF for 5 hrs, after which the
reaction mixture was transferred to a 500 mL
separatory funnel containing 100 mL water and
extracted with 50 mL chloroform. The organic
layer was washed twice with 100 mL water, the
solvent was evaporated under reduced pressure,
and the crude product was purified by washing 3
times in 75 mL hot ethanol. Filtration of the so
lids and removal of remain
ing solvent under reduced
pressure gave analytically pure
14
as ultra-fine, white needles
(3.1 g, 6.6 mmol, 72% yield).
1
H
NMR (300 MHz, CDCl
3
):
δ
= 8.03 (d, 2 carbazole H,
J
= 7.8 Hz), 7.43-7.14 (m, 4 carbazole H and
15 phenyl H), 7.00 (d, 2 carbazole H,
J
= 8.1 Hz), 4.06 (t, NC
H
2
,
J
= 8.1 Hz), 2.75 (t, SC
H
2
,
J
= 8.1
Hz).
13
C NMR (300 MHz, CDCl
3
):
δ
= 144.61, 139.76, 129.69,
128.01, 126.86, 125.56, 122.79,
120.27, 119.00, 108.54, 67.39, 42.37, 30.22.
Functionalization Procedure and Results.
To compound
14
(0.25 g, 0.5 mmol) dissolved in 10
mL chloroform in a 100 mL Schlenk tube were
added triethylsilane (A
lfa Aesar, 98%, 0.08 g, 0.7
mmol) and trifluoroacetic acid (TFA, 0.5 mL, 5 %vol), and the mixture
was stirred 1-2 hrs at r.t.
After addition of 1,2-PB (0.2 g,
4 mmol vinyl groups, dissolved in
10 mL chloroform) and AIBN
(0.03 g, 0.2 mmol), the contents of the Schlenk tube
were degassed in 3 freeze-pump-thaw cycles,
then allowed to react at 55
o
C for 3 hrs. Following reaction, the polymer solution was transferred to
a 100 mL jar containing a small amount of BHT, con
centrated by evaporation of all but the last 10
mL solvent under an argon stream, and precipitated
in cold methanol. Final purification of the
polymer was achieved by reprecipitation from a DC
M solution with cold methanol (2-3 times),
followed by drying to constant weight under vacuum
at r.t. Reaction conditions and results for a
specific example are given in Table A.1 (first entry).
4. 1,2-Polybutadiene Functionalization Using Thiobenzoic acid S-[3-(9-carbazolyl)propyl]
ester (16)
Synthesis of 9-Allylcarbazole (15).
Carbazole (10.1 g, 0.057 mol)
and potassium hydroxide (88 %
wt pellets, crushed, 7.1 g, 0.11 mol) we
re stirred in 100 mL DMSO at 50
o
C for 30 min before
dropwise addition of allyl bromide (14.7 g, 0.118 mo
l). After 15 min the
reaction mixture was
poured into a 500 mL separatory funnel containing 100 mL chloroform and washed 5 times with
200 mL water to give, after solvent evaporation at 60
o
C under reduced pressure, compound
15
in >
99% purity as a dark brown, viscous syrup wh
ich solidified upon coolin
g (11.9 g, 0.057 mol, 100%
yield).
1
H NMR (300 MHz, CDCl
3
):
δ
= 8.14-8.06 (m, 2 carbazole H), 7.49-7.32 (m, 4 carbazole
H), 7.28-7.19 (m, 2 carbazole H), 6.04-5.90 (m, C
H
=CH
2
), 5.19-5.10 (m, Z-
H
CH=CH), 5.07-4.97
(m, E-
H
CH=CH), 4.92-4.85 (m, NC
H
2
).
13
C NMR (300 MHz, CDCl
3
):
δ
= 140.34, 132.27, 125.67,
122.90, 120.33, 119.00, 116.74, 108.74, 45.21.
Synthesis of Thiobenzoic acid S-[3-(9-carbazolyl)propyl] ester (16).
Thiobenzoic acid (30 g,
0.20 mol) was added to 9-allylcarbazole (11.9 g,
0.057 mol) in 100 mL toluene, and the reaction
was carried out at 90
o
C with argon purge via radical mechanis
m using AIBN as the initiator (1.8 g,
11 mmol, in 300 mg increments at
1 hr intervals). After 6 hrs the reaction mixture was poured into
a 1 L separatory funnel containing 20 g sodium bicarbonate (NaHCO
3
, 0.24 mol) in 250 mL water,
extracted with 100 mL chloroform, and the orga
nic phase was washed twice with 200 mL water
before solvent removal under reduced pressure. The crude product was subsequently washed in 100
mL hot hexane, 150 mL ethanol, and finally 150 mL
of 15:1 ethanol:chloroform. Evaporation of
leftover solvent at 80
o
C under reduced pressure yielded compound
16
in ca. 90% purity as a dark
brown, viscous syrup which solidified upon c
ooling (9.35 g, 0.024 mol, 42% yield, ~ 10 %wt
dibenzoyl disulfide).
1
H NMR (300 MHz, CDCl
3
):
δ
= 8.10 (d, 2 carbazole H,
J
= 8.1 Hz), 8.00-
7.95 (m, 2 aromatic H
ortho
to COS), 7.62-7.41 (m, 3 aromatic H
meta
and
para
to COS plus 4
carbazole H), 7.27-7.19 (m, 2 carbazole H), 4.43 (t, NC
H
2
,
J
= 6.9 Hz), 3.06 (t, SC
H
2
,
J
= 6.9 Hz),
2.26 (tt, NCH
2
C
H
2
CH
2
S,
J
= 6.9, 6.9 Hz).
13
C NMR (300 MHz, CDCl
3
):
δ
= 191.56, 140.25,
136.88, 133.50, 128.65, 127.23, 125.75, 122.91, 120.41, 119.00, 108.55, 41.65, 28.95, 26.41.
Functionalization Procedure and Results.
The functionalization proc
edure followed the general
method outlined in the experimental section. Reac
tion conditions and results for a specific example
are given in Table A.1 (second entry).
Table A1. Reaction Conditions and Results for 1,2-PB Functiona
lization Using Compounds 14 and 16
Entry
a
[PB]
[Thiol]
b
[AIBN]
Rxn time
X
funct
c
M
W
d
PDI
d
New H NMR peaks above 2.2 ppm for modified PB
(g/mL)
(g/mL)
(hrs)
%
(kg/mol)
(all peaks are broad)
820kPB14
0.011
0.1
0.002
2.9
6
945
2.08
8.12-8.04 (2H), 7.52-7.39 (4H), 7.27-7.19 (2H), 4.56-4.43 (2H), 2.97-2.83 (2H)
92kPB16
0.003
1.1
0.003
3.0
19
187
1.34
8.15-8.03 (2H), 7.56.-7.37 (4H), 7.28-7.15 (2H), 4.50-4.27(2H), 2.62-2.30 (4H)
a)
Modified PB polymers were named so that the prefix corresponds
to the molecular weight of the starting 1,2-PB chain, and the su
ffix
represents the reagent used.
b)
In molar equivalents of 1,2-PB monomer units.
c)
The fraction of reacted 1,2-PB
units that bear functional groups
(refer to text).
d)
Measurements as described in Experiment
al section using the Waters setup (the 1,2-
PB prepolymers had PDI values of 1.07 and
1.26 for the 92 kg/mol and 820 kg/mol chains, respectively.