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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: [email protected] (Y. Morisaki) [email protected] (Y. Chujo) Contents: page General S-2 Materials S-3 Synthesis and characterization Synthesis of (R p )-3 and (S p )-3 S-4 Synthesis of (R p )-4 and (S p )-4 S-7 Synthesis of polymer (R p )-P1 and (S p )-P1 S-10 Photoluminescence (PL) decay studies S-12 Optimized structure of the model compound in the excited state by TD-DFT S-13 S-1

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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: [email protected] (Y. Morisaki)

[email protected] (Y. Chujo)

Contents: pageGeneral S-2Materials S-3Synthesis and characterization Synthesis of (Rp)-3 and (Sp)-3 S-4 Synthesis of (Rp)-4 and (Sp)-4 S-7 Synthesis of polymer (Rp)-P1 and (Sp)-P1 S-10Photoluminescence (PL) decay studies S-12Optimized structure of the model compound in the excited state by TD-DFT S-13References S-14

S-1

General

1H and 13C 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). Specific rotations ([]tD)

were measured with a HORIBA SEPA-500 polarimeter. 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.

S-2

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

S-3

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. After MgSO4 was

removed by filtration, solvent was removed by a rotary evaporator. 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). 1H 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), (m, 2H), 7.33 (dd, J = 5.1 and 1.1 Hz, 2H) ppm; 13C NMR

(CDCl3, 100 MHz): 33.9, 35.2, 125.2, 125.4, 127.3, 130.4, 132.0, 134.1, 135.6, 136.8, 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). []23D = 39.3 (c 0.25, CHCl3).

S-4

rac-3

enantiopure (Rp)-3

enantiopure (Sp)-3

Column: Chiralpak® IA, 0.46 cm 25 cm Eluent: hexane/i-PrOH = 150/1 v/vFlow 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.

S-5

Figure S2. 1H NMR spectrum of (Rp)-3, 400 MHz, CDCl3.

Figure S3. 13C NMR spectrum of (Rp)-3, 100 MHz, CDCl3.

S-6

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). 1H 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. HRMS (APCI)

calcd. for C24H19Br2S2 [M+H]+: 528.9289, found 528.9293. []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).

S-7

rac-4

enantiopure (Rp)-4

enantiopure (Sp)-4

Column: Chiralpak® IA, 0.46 cm 25 cm Eluent: hexane/i-PrOH = 50/1 v/vFlow 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.

S-8

Figure S5. 1H NMR spectrum of (Rp)-4, 400 MHz, CDCl3.

Figure S6. 13C NMR spectrum of (Rp)-4, 100 MHz, CDCl3.

S-9

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%).

1H 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%).

S-10

Figure S7. 1H NMR spectrum of (Rp)-P1, 400 MHz, CDCl3.

Figure S8. 13C NMR spectrum of (Rp)-P1, 100 MHz, CDCl3.

S-11

Time calibration: 5.5396 × 10–2 ns/ch

= 0.62 ns, 2 = 1.04

Figure S9. PL decay at 510 nm and data of (Rp)-P1 in CHCl3 (1.0 × 10–5 M) excited at 375 nm.

Time calibration: 5.5396 × 10–2 ns/ch

= 0.64 ns, 2 = 1.06

Figure S10. PL decay at 510 nm and data of (Sp)-P1 in CHCl3 (1.0 × 10–5 M) excited at 375 nm.

S-12

Figure S11. Optimized structure of the (Sp)-model compound in the excited state by time-

dependent density functional theory (PBE1PBE/6-31G(d)).

S-13

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.

S-14