Supporting Information
Synthesis of Optically Active Through-space Conjugated Polymers Consisting of Planar
Chiral [2.2]Paracyclophane and Quaterthiophene
Yasuhiro Morisaki,* Kenichi Inoshita, Shotaro Shibata and Yoshiki Chujo*
Department or Polymer Chemistry, Graduate School of Engineering, Kyoto University
Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
E-mail:
ymo@chujo.synchem.kyoto-u.ac.jp (Y. Morisaki)
chujo@chujo.synchem.kyoto-u.ac.jp (Y. Chujo)
Contents:
General
Materials
Synthesis and characterization
Synthesis of (Rp)-3 and (Sp)-3
Synthesis of (Rp)-4 and (Sp)-4
Synthesis of polymer (Rp)-P1 and (Sp)-P1
Photoluminescence (PL) decay studies
Optimized structure of the model compound in the excited state by TD-DFT
References
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page
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General
1
H and
13
C spectra were recorded on a JEOL EX400 or AL400 instrument at 400 and 100
MHz, respectively.
Samples were analyzed in CDCl3, and the chemical shift values were
expressed relative to Me4Si as an internal standard.
Analytical thin layer chromatography (TLC)
was performed with silica gel 60 Merck F254 plates.
Column chromatography was performed with
Wakogel C-200 or C-300 SiO2.
Optical resolution by column chromatography was carried out
using a HPLC (TOSOH UV-8020) equipped with a Chiralpak® IA column (0.46 cm  25 cm, flow
rate 0.5 mL/min).
Gel permeation chromatography (GPC) was carried out on a TOSOH 8020
(TSKgel G3000HXL column) instrument using CHCl3 as an eluent after calibration with standard
polystyrene samples.
Recyclable preparative high performance liquid chromatography (HPLC)
was carried out on a Japan Analytical Industry Model LC918R (JAIGEL 1H and 2H columns) using
CHCl3 as an eluent.
High-resolution mass (HRMS) spectrometry was performed at the Technical
Support Office, Department of Synthetic Chemistry and Biological Chemistry, Graduate School of
Engineering, Kyoto University).
HRMS spectra were obtained on a Thermo Fisher Scientific
EXACTIVE spectrometer for atmospheric pressure chemical ionization (APCI).
UV-vis spectra
were recorded on a SHIMADZU UV-3600 spectrophotometer, and samples were analyzed in CHCl3
at room temperature.
Photoluminescence (PL) spectra were recorded on a HORIBA JOBIN
YVON Fluoromax-4 spectrofluorometer, and samples were analyzed in CHCl3 at room temperature.
PL lifetime measurement was performed on a Horiba FluoreCube spectrofluorometer system;
excitation was carried out using a UV diode laser (NanoLED 375 nm).
were measured with a HORIBA SEPA-500 polarimeter.
Specific rotations ([]tD)
Circular dichroism (CD) spectra were
recorded on a JASCO J-820 spectropolarimeter with CHCl3 as a solvent at room temperature.
Circularly polarized luminescence (CPL) spectra were recorded on a JASCO CPL-200S with CHCl3
as a solvent at room temperature.
Elemental analyses were performed at Organic Elemental
Analysis Research Center, Kyoto University.
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Materials
Commercially available compounds used without purification:
Pd2(dba)3
2-Thiopheneboronic acid
PCy3HBF4
P(t-Bu)3HBF4
K3PO3
N-Bromosuccinimide (NBS)
Commercially available solvents:
1,4-Dioxane (dehydrated), used without purification
THF and NEt3, purified by passage through solvent purification columns under Ar pressure.1
Compounds prepared as described in the literatures:
(Rp)- and (Sp)-Pseudo-ortho-diiodo[2.2]paracyclophanes,2 (Rp)- and (Sp)-2
2,2'-(3,3'-Didodecyl-[2,2'-bithiophene]-5,5'-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane),3 5
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Synthesis of (Rp)-3 and (Sp)-3
The mixture of (Rp)-pseudo-ortho-diiodo[2.2]paracyclophane (Rp)-2 (46.0 mg, 0.10 mmol),
2-thiopheneboronic acid (38.4 mg, 0.30 mmol), Pd2(dba)3 (9.2 mg, 0.010 mmol), PCy3HBF4 (14.7
mg, 0.040 mmol), and K3PO4 (191.0 mg, 0.90 mmol) was placed in a Schlenk tube equipped with a
magnetic stirrer bar and a reflux condenser.
The equipment was purged with Ar, following by
adding 1.4-dioxane (1.5 mL) and H2O (0.5 mL).
The reaction was carried out at 100 °C for 40 h.
The reaction mixture was poured into water, and organic species were extracted three times with
CHCl3. The organic layer was washed with brine, and dried over MgSO4.
removed by filtration, solvent was removed by a rotary evaporator.
After MgSO4 was
The residue was purified by
column chromatography on SiO2 (eluent: hexane/toluene = 4/1 v/v) to give (Rp)-3 (29.6 mg, 0.079
mmol, 79%) as a colorless oil.
Rf = 0.3 (hexane/toluene = 4/1 v/v).
1
H NMR (CDCl3, 400 MHz): 
(m, 4H), 3.08
(m, 2H), 3.79 (m, 2H), 6.58 (dd, J = 7.7 and 1.7 Hz, 2H), 6.67 (d, J = 7.7 Hz, 2H), 6.81 (d, J = 1.7
Hz, 2H), 7.05 (dd, J = 3.5 and 1.1 Hz, 2H),
J = 5.1 and 1.1 Hz, 2H) ppm;
C NMR (CDCl3, 100 MHz):  33.9, 35.2, 125.2, 125.4, 127.3, 130.4, 132.0, 134.1, 135.6, 136.8,
13
139.8, 143.5 ppm.
HRMS (APCI) calcd. for C24H21S2 [M+H]+: 373.1079, found 373.1076.
[]23D = –39.6 (c 0.25, CHCl3).
Elemental Analysis calcd. for C24H20S2: C 77.38, H 5.44 %, found
C 77.15, H 5.44 %.
The synthetic procedure of (Sp)-3 is the same as that of (Rp)-3, which was obtained in 90%
yield (33.7 mg, 0.090 mmol) from (Sp)-2 (46.0 mg, 0.10 mmol).
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[]23D = 39.3 (c 0.25, CHCl3).
rac-3
10
11
12
13
14
15
16
Elution time / min
17
18
19
20
13
14
15
16
Elution time / min
17
18
19
20
13
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15
16
Elution time / min
17
18
19
20
enantiopure (Rp)-3
10
11
12
enantiopure (Sp)-3
10
11
12
Column: Chiralpak® IA, 0.46 cm  25 cm
Eluent: hexane/i-PrOH = 150/1 v/v
Flow rate: 0.5 mL/min
Figure S1. Chromatographic optical resolution of rac-3; absolute configuration was confirmed by
chromatograms of enantiopure (Rp)-3 and (Sp)-3.
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Figure S2.
1
Figure S3.
13
H NMR spectrum of (Rp)-3, 400 MHz, CDCl3.
C NMR spectrum of (Rp)-3, 100 MHz, CDCl3.
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Synthesis of (Rp)-4 and (Sp)-4
The mixture of (Rp)-3 (29.6 mg, 0.079 mmol) and NBS (35.6 mg, 0.20 mmol) was placed in a
Schlenk tube equipped with a magnetic stirrer bar.
The equipment was purged with Ar, following
by adding CHCl3 (10 mL). The reaction was carried out at room temperature for 12 h. The
solvent was removed by a rotary evaporator.
The residue was purified by column chromatography
on SiO2 (eluent: hexane/CHCl3 = 9/1 v/v) to give (Rp)-4 (31.2 mg, 0.059 mmol, 74%) as a colorless
oil.
Rf = 0.25 (hexane/ CHCl3 = 9/1 v/v).
1
H NMR (CDCl3, 400 MHz): 
(m, 4H), 3.09
(m, 2H), 3.72 (m, 2H), 6.59 (dd, J = 7.7 and 1.6 Hz, 2H), 6.65 (d, J = 7.7 Hz, 2H), 6.70 (d, J = 1.6
Hz, 2H),
(d, J = 3.8 Hz, 2H), 7.06 (d, J = 3.8 Hz, 2H) ppm; 13C NMR (CDCl3, 100 MHz):
33.9, 35.0, 111.7, 125.6, 129.9, 130.3, 132.4, 133.3, 135.8, 136.7, 139.9, 144.9 ppm.
(APCI) calcd. for C24H19Br2S2 [M+H]+: 528.9289, found 528.9293.
HRMS
[]23D = 89.48 (c 0.25,
CHCl3). Elemental Analysis calcd. for C24H18Br2S2: C 54.35, H 3.42 %, found C 53.94, H 3.42 %.
The synthetic procedure of (Sp)-4 is the same as that of (Rp)-4, which was obtained in 98%
yield (20.8 mg, 0.039 mmol) from (Sp)-3 (14.9 mg, 0.040 mmol). []23D = –89.49 (c 0.25, CHCl3).
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rac-4
10
11
12
13
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15
16
Elution time / min
17
18
19
20
13
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15
16
Elution time / min
17
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20
13
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15
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Elution time / time
17
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enantiopure (Rp)-4
10
11
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enantiopure (Sp)-4
10
11
12
Column: Chiralpak® IA, 0.46 cm  25 cm
Eluent: hexane/i-PrOH = 50/1 v/v
Flow rate: 0.5 mL/min
Figure S4. Chromatographic optical resolution of rac-4; absolute configuration was confirmed by
chromatograms of enantiopure (Rp)-4 and (Sp)-4.
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Figure S5.
1
Figure S6.
13
H NMR spectrum of (Rp)-4, 400 MHz, CDCl3.
C NMR spectrum of (Rp)-4, 100 MHz, CDCl3.
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Synthesis of polymer (Rp)-P1 and (Sp)-P1
The mixture of Pd2(dba)3 (3.7 mg, 0.020 mmol), P(t-Bu)3·HBF4 (5.8 mg, 0.020 mmol), K3PO4
(42.5 mg, 0.200 mmol), compound (Rp)-4 (10.6 mg, 0.020 mmol), and compound 5 (15.1 mg, 0.020
mmol) was dissolved in THF (1.0 mL) and H2O (1.0 mL) at room temperature under Ar atmosphere.
The reaction mixture was stirred at 70 °C (oil bath temperature) under Ar atmosphere for 48 h.
After cooling to room temperature, H2O and CHCl3 were added, and the organic species were
extracted with CHCl3. The organic layer was dried over MgSO4. After MgSO4 was removed,
the solvent was evaporated. The residue was purified by high performance liquid chromatography
(HPLC) with CHCl3 as an eluent to obtain polymer (Rp)-P1 as an orange powder (10.3 mg, 0.012
mmol, 59%).
1
H NMR (CDCl3, 400 MHz):  0.83 (m, 6H), 1.23 (m, 36H), 1.60 (m, 4H), 2.55 (m, 4H), 2.91
(br, 4H), 3.11 (br, 2H), 3.89 (br, 2H), 6.59 (br, 2H), 6.66 (br, 2H), 6.85 (br, 2H), 6.99 (br, 2H), 7.08
(br, 2H), 7.17 (br, 2H) ppm; 13C NMR (CDCl3, 100 MHz): 14.1, 22.7, 29.5 (m), 30.7, 31.9, 33.9,
35.4, 123.9, 125.0, 126.2, 127.3, 130.0, 132.1, 133.9, 136.0, 137.2 (m), 140.0, 142.4, 143.5 ppm.
Polymer (Sp)-P1 was obtained by the same procedure (8.7 mg, 0.010 mmol, 50%).
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Figure S7.
1
Figure S8.
13
H NMR spectrum of (Rp)-P1, 400 MHz, CDCl3.
C NMR spectrum of (Rp)-P1, 100 MHz, CDCl3.
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1 x 105
Time calibration: 5.5396 × 10–2 ns/ch
1x
104

 = 0.62 ns, 2 = 1.04
Counts
1 x 103
100
10
1
150
200
250
300
350
400
channel
Figure S9.
PL decay at 510 nm and data of (Rp)-P1 in CHCl3 (1.0 × 10–5 M) excited at 375 nm.
1 x 105
Time calibration: 5.5396 × 10–2 ns/ch
1 x 104

 = 0.64 ns, 2 = 1.06
Counts
1 x 103
100
10
1
150
200
250
300
350
400
channel
Figure S10.
PL decay at 510 nm and data of (Sp)-P1 in CHCl3 (1.0 × 10–5 M) excited at 375 nm.
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Figure S11.
Optimized structure of the (Sp)-model compound in the excited state by
time-dependent density functional theory (PBE1PBE/6-31G(d)).
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References
1
Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J.
Organometallics 1996, 15, 1518–1520.
2
Morisaki, Y.; Inoshita, K.; Chujo Y. Chem.–Eur. J. 2014, 20, 8386–8390.
3
Yoshii, R.; Tanaka, K.; Chujo, Y. Macromolecules 2014, 47, 2268-2278.
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