Supporting Information
Magnetically Recyclable Pd-Fe3O4 Heterodimer Nanocrystals for The
Synthesis of Conjugated Polymers via Suzuki Polycondensation: Toward
Green Chemistry
Ilhak Bae,† In-Hwan Lee,† Sangmoon Byun, Jooyoung Chung, B. Moon Kim* and Tae-Lim Choi*
Department of Chemistry, Seoul National University, Seoul 151-747, Korea.
E-mail : kimbm@snu.ac.kr, tlc@snu.ac.kr
S1
Table of contents
1. General experimental, materials, and preparation of Pd-Fe3O4 HNCs --------------------------------- S3
2. Experimental procedures for the preparation of polymers ----------------------------------------------- S3
3. Condition optimization for Suzuki polymerization ------------------------------------------------------- S4
4. Polymerization using dibromo compounds, and diiodo compounds containing long or many of
aliphatic side chains ---------------------------------------------------------------------------------------------- S5
5. Recycling of the Pd-Fe3O4 HNC catalyst with and without sonication process ---------------------- S5
6. Pd(PPh3)4, Pd2(dba)3-catalyzed Suzuki polymerization -------------------------------------------------- S6
7. 1H NMR spectra of polymers ---------------------------------------------------------------------------- S6-S7
8. SEC traces of polymers ----------------------------------------------------------------------------------- S8-S9
S2
Experimental details
General experimental
NMR spectra were recorded by Varian/Oxford As-500 (500 MHz for 1H, 125 MHz for 13C). THF Gel
permeation chromatography (GPC) for polymer molecular weight analysis was carried out with Waters system
(1515 pump, 2414 refractive index detector and 2489 UV detector) and Shodex GPC LF-804 column eluted
with THF (GPC grade, Honeywell Burdick & Jackson). Flow rate was 1.0 mL/min and temperature of column
was maintained at 35 °C. Samples were diluted in 0.001-0.005 wt% by THF and filtered with a 0.20 μm PTFE
filter before injection into the GPC. Sonication was carried out with Powersonic 410 model devices from
Hwashin Tech. Inductively coupled plasma mass spectrometry (ICP-MS) was performed by using ICPS-7500
spectrometer (Shimadzu).
Materials
Without additional notes, all reagents were commercially available and used without further purification. THF
was distilled over sodium and benzophenone, and degassed by argon bubbling for 10 minutes before using on
polymerization. Toluene, 1,4-dioxane, methanol, DMF were purified by solvent purification system using
alumina column, and degassed by argon bubbling. N,N’ -dimethylacetamide (DMA) was purchased from Junsei
and degassed by argon for 10 minutes before using on polymerization without further purification.
Preparation of Pd-Fe3O4 HNCs
The Pd-Fe3O4 HNCs were prepared according to the previously reported
procedure.S1 The synthesis was performed by one-pot thermal degradation of a
mixture solution composed of iron acetylacetonate (14.0g, 40.0 mmol), palladium
acetylacetonate (200 mg, 0.066 mmol), oleylamine (120 mL, 350 mmol), and
oleic acid (80 mL, 250 mmol). The mixture was heated to 120 °C under reduced
pressure while being vigorously stirred for 2 h. The resulting mixture was heated
to 220 °C under Argon at a heating rate of 2 °C/min and kept at same temperature
for 30 min. Then it was further heated to 300 °C at the 2 °C/min heating rate and
aged for 30 min. Next the mixture was cooled to room temperature and washed
with ethanol and a black supernatant was sore. The residue was dispersed in
EtOH through sonication and products were collected by centrifugation (1750
rpm, 15 min). The Pd–Fe3O4 product was again dispersed in hexane and collected through the use of
centrifugation (1750 rpm, 15 min). This washing process was rerun until the sore hexane did not show any color.
Then, the Pd-Fe3O4 HNCs was collected and dried under vacuum to provided 2.45 g of dark solid.
General preparation of polymers
: The mixture of 1 equiv of diiodo compounds (0.3 mmol), 1 equiv of diboronic acid (or diboronic ester)
compounds (0.3 mmol), 5 equiv of base (1.5 mmol), 2 mol% of Pd-Fe3O4 (2 mol% loading of Pd-atom
equivalents, 26 mg of 2.45 wt% Pd–Fe3O4) in Schlenk tube was evacuated and backfilled with argon four times,
then degassed solvent (2-3 ml, 0.10-0.15 M) was added to the reaction mixture. The Schlenk tube was tightly
sealed, and it was sonicated for 30 min at room temperature. The reaction mixture was immersed in 70 C (or
110 C) oil bath and stirred for 72 hr with stirring. The reaction mixture was cooled down to room temperature,
and the Pd-Fe3O4 catalyst was separated using a magnet. The resulting reaction mixture was diluted with
chloroform, and washed with brine. The combined organic layers were dried with magnesium sulfate, and
concentrated. The concentrated solution was precipitated into methanol, filtered, and dried under vacuum. The
recovered Pd-Fe3O4 catalyst was washed many times by using chloroform, hexane, water, acetone, and
tetrahydrofuran then it was dried and reused for the next run of the reaction.
Poly(2,7-(9,9-di(2’-ethylhexyl)fluorene)-alt-1,4-phenylene) (Table 1)
: This polymer was already reported.S3 The 1H NMR data is also available in the same literature.
Poly(2,7- (9,9-dioctylfluorene) -alt-1,4-phenylene) (Table 2, entry 2)
: This polymer was already reported.S2 The 1H NMR data is also available in the same literature.
Poly(2,7- (9,9-dioctylfluorene) -alt-4,4'-biphenylene) (Table 2, entry 3)
: This polymer was already reported.S2 The 1H NMR data is also available in the same literature.
Poly(2,7- (9,9-di(2’ -ethylhexyl)fluorene) -alt-2,5-thiophene) (Table 2, entry 6)
: This polymer was already reported.S3 The 1H NMR data is also available in the same literature.
S3
References
(S1) Jang, Y.; Chung, J.; Kim, S.; Jun, S. W.; Kim, B. H.; Lee, D. W.; Kim, B. M.; Hyeon, T. Phys. Chem. Chem. Phys.,
2011, 13, 2512.
(S2) Ranger, M.; Leclerc, M. Can. J. Chem., 1998, 76, 1571.
(S3) Charas, A.; Morgado, J.; Martinho, J. M. G.; Alcácer, L.; Lim, S.F.; Friend, R. H.; Cacialli, F. Polymer, 2003, 44, 1843.
Table S1. Condition optimization for Suzuki polymerization
entry
Solvent
base
time
(hr)
temp
(C)
1
THF
Na2CO3 (5 eq)
72
110
trace amount
2
THF
K2HPO4 (5 eq)
72
110
trace amount
3
THF
KOAc (5 eq)
72
110
trace amount
4
THF (0.15M)
K3PO4 (5 eq)
72
110
5
THF
K3PO4 (3 eq)
72
110
6
THF (0.15M)
K3PO4 (5 eq)
72
70
15.6k
56.7k
3.63
95%
7b,c
THF (0.15M)
K3PO4 (5 eq)
72
110
12.7k
53.3k
4.20
94%
8d
THF (0.15M)
K3PO4 (5 eq)
72
110
n.d.
9e
THF (0.15M)
K3PO4 (5 eq)
72
70
no precipitates
10
1,4-dioxane
K3PO4 (5 eq)
72
105
13.0k
32.8k
2.52
84%
11
DMF
K3PO4 (5 eq)
72
160
4.3k
8.9k
2.07
31%
12
Toluene
K3PO4 (5 eq)
72
100
13f
toluene/H2O(v/v=3/1)
K3PO4 (5 eq)
72
100
14f
toluene/H2O(v/v=1/1)
K2CO3 (10 eq)
72
100
n.d.
24%
15f
toluene/H2O(v/v=1/1)
Na2CO3 (10 eq)
72
100
n.d.
29%
16
THF/H2O(v/v=3/1)
K3PO4 (5 eq)
72
100
7.0k
13.3k
1.90
87%
17b
THF/H2O(v/v=3/1)
K2CO3 (5 eq)
48
100
8.1k
27.2k
3.36
76%
18b
THF/H2O(v/v=3/1)
Cs2CO3 (5 eq)
48
100
2.7k
7.1k
2.63
73%
19
THF/MeOH(v/v=4/1)
Cs2CO3 (5 eq)
72
100
20b
THF/DMA(v/v=4/1)
K3PO4 (5 eq)
72
110
21
THF/H2O (v/v=14/1)
K3PO4 (5 eq)
72
110
22
1,4-dioxane/H2O(v/v=3/1)
K2CO3 (5 eq)
48
90
23b
1,4-dioxane/H2O(v/v=3/1)
Cs2CO3 (5 eq)
48
90
2.2k
6.1k
2.77
78%
24b
DMA/H2O(v/v=4/1)
K2CO3 (5 eq)
72
100
1.9k
7.5k
3.95
83%
25b
DMA/H2O(v/v=4/1)
K3PO4 (5 eq)
72
100
0.8k
2.63
46%
a Determined
Mna
15.2k
Mwa
41.4k
PDIa
2.72
yield
96%
trace amount
13%
no precipitates
4.8k
11.2k
2.33
n.d.
3.4k
15.4k
49%
36%
4.53
86%
no precipitates
n.d.
b Determined
2.1k
29%
by THF SEC calibrated using PS standards. Mn is given in g/mol.
by CHCl3 SEC calibrated using
PS standards. Mn is given in g/mol. c 5 mol% of Pd-Fe3O4 was used. d 0.5 mol% of Pd-Fe3O4 was used. e Fe3O4 was used
rather than Pd-Fe3O4. f A drop of Aliquat 336 was added.
S4
Table S2. Polymerization using dibromo compounds, and diiodo compounds containing
long or many of aliphatic side chains
Mna
PDIa
yield
1
2.5k
1.20
80%
2b
4.3k
1.58
90%
entry
a Determined
monomers
3
trace amount
4
trace amount
5
trace amount
6
n.d.
13%
by THF SEC calibrated using PS standards. Mn is given in kg/mol. b Reaction was run at 110 C.
Table S3. Recycling of the Pd-Fe3O4 HNC catalyst with and without sonication process
(a) recycling at 70 C (w/ sonication)
run
1
2
3
4
5
6
7
8
9
10
11
temp.
(oC)
70
70
70
70
70
70
70
70
70
70
70
Mna
PDIa
yield
17.6k
14.2k
8.6k
12.6k
11.3k
6.2k
7.0k
21.5k
14.1k
21.8k
15.1k
4.03
3.12
2.34
4.93
2.42
3.82
4.53
3.05
3.43
7.99
2.14
>99%
95%
95%
77%
>99%
34%
52%
81%
65%
82%
>99%
(b) recycling at 110 C (w/ sonication)
ICP-MS
(ppm)
38
17
38
28
31
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
run
1
2
3
4
5
6
7
8
9
10
temp.
(oC)
110
110
110
110
110
110
110
110
110
110
Mna
PDIa
yield
8.2k
15.9k
11.9k
8.1k
4.3k
13.0k
9.2k
5.8k
9.1k
14.6k
2.37
2.83
2.94
2.19
1.58
3.12
2.78
2.00
2.24
3.14
80%
94%
87%
90%
47%
86%
80%
56%
68%
85%
ICP-MS
(ppm)
56
3
24
4
n.d.
21
n.d.
n.d.
n.d.
n.d.
(c) recycling at 70 C (w/o sonication)
ICP-MS
(ppm)
15.6k
3.63
95%
53
1
70
(22.6k)b
(2.44)b
(84%)b
(32)b
2
70
n.d.
26%
n.d.
3
70
n.d.
17%
n.d.
a Determined by THF SEC calibrated using PS standards. M is given in g/mol. b Determined after Soxhlet extraction with
n
methanol and acetone.
run
temp.
(oC)
Mna
PDIa
yield
S5
Table S4. Pd(PPh3)4, Pd2(dba)3-catalyzed Suzuki polymerization
entry
solvent
Pd(PPh3)4
loading
Base
time
(hr)
temp
(C)
Mna
PDIa
yield
ICP-MS
(ppm)
1
THF (0.15 M)
2 mol%
K3PO4 (5 eq)
72
70
4.3k
1.88
73%
1996
Mna
PDIa
yield
8.5k
(9.9k)b
2.76
(2.66)b
69%
(62%)b
a Determined
by THF SEC calibrated using PS standards. Mn is given in g/mol
entry
solvent
Pd2(dba)3
loading
Base
2
toluene (0.15 M)
2 mol%
Et4NOH (7 eq)
a Determined
b Determined
time
(hr)
temp
(C)
87
110
by THF SEC calibrated using PS standards. Mn is given in g/mol
after Soxhlet extraction with methanol and acetone.
Figure S1. 1H NMR spectra of polymers
Poly(2,7-(9,9-didodecylfluorene)-alt-1,4-phenylene) (Table 2, entry 1 (CDCl3))
S6
ICP-MS
(ppm)
151
(101)b
Poly(2,7-(9,9-dioctylfluorene)-alt-2,7-(9,9-dimethylfluorene)) (Table 2, entry 4 (CDCl3))
Poly(2,7-(9,9-didodecylfluorene)-alt-1,3-phenylene) (Table 2, entry 5 (CDCl3))
Poly(2,7-(9,9-didodecylfluorene)-alt-2,2’-bithiophene) (Table 2, entry 7 (CDCl3))
S7
Figure S2. SEC traces of polymers
8
Table 2, entry 2
Table 2, entry 3
RI Intensity (a.u.)
RI Intensity (a.u.)
6
4
2
0
-2
10
15
5
0
10
20
4
Table 2, entry 4
RI Intensity (a.u.)
RI Intensity (a.u.)
10
5
0
10
15
20
Table 2, entry 5
2
0
-2
10
20
15
20
Retention Time (min)
Retention Time (min)
4
Table 2,entry 6
Table 2, entry 7
3
RI Intensity (a.u.)
6
RI Intensity (a.u.)
15
Retention Time (min)
Retention Time (min)
3
0
2
1
0
-1
10
15
10
20
Retention Time (min)
5
6
Table 3, run 2
20
Table S3 (a), run 1
4
3
RI Intensity (a.u.)
RI Intensity (a.u.)
4
2
1
0
-1
-2
10
15
Retention Time (min)
15
Retention Time (min)
2
0
-2
-4
10
20
15
20
Retention Time (min)
S8
3
Table S4, Pd(PPh3)4
8
RI Intensity (a.u.)
RI Intensity (a.u.)
10
6
4
2
Table S4, Pd2dba3
2
1
0
0
-2
10
15
-1
10
20
Retention Time (min)
15
20
Retention Time (min)
S9