Supporting Information

Poly(arylene sulfone)s Containing 9,9’-Spirobifluorene: Synthesis and Excellent Optical Properties

Hitoshi OKUDA, Ryota SETO, Yasuhito KOYAMA, and Toshikazu TAKATA†,

1Department of Organic and Polymeric Materials, Tokyo Institute of Technology

Ookayama, Meguro, Tokyo 152-8552, Japan

†To whom correspondence should be addressed (Tel: +81-3-5734-3260, FAX: +81-3-5734-2888, E-mail: )

RUNNING HEAD: 9,9’-Spirobifluorene-containing Poly(arylene sulfone)s

Table of content:

Synthesis and UV-vis spectra of mono(arylene thioether) MTE and mono(arylene sulfone) MAS.

1H-NMR, FT-IR spectra for all new compounds.
Synthesis of mono(arylene thioether) MTE and mono(arylene sulfone) MAS.

Synthesis of MTE

9,9'-Spirobifluorene-2,2'-bis(N,N-dimethylcarbamothioate) 1 (0.157 g, 0.300 mmol), 4-fluorobenzophenone 2 (0.097 g, 0.300 mmol), Cs2CO3 (0.048 g, 0.150 mmol), CaCO3 (0.090 g, 0.900 mmol), and diphenylsulfone (0.9 g) were equipped with a 30 mL two-necked round-bottom flask under argon atmosphere. The mixture was heated to 200 °C and kept at the same temperature for 2 h. The temperature was raised to 240 °C and kept at the temperature for 7 h. The resulting mixture was cooled to room temperature, quenched by the addition of acetic acid (0.5 mL), and then poured into MeOH to precipitate as yellow solids. The precipitates were collected by filtration and washed with MeOH. The crude polymer was dissolved with CHCl3 and the solution was filtrated through Celite pad. The solution was reprecipitated into MeOH, and collected by filtration to give MTE as yellow solids in 45% yield (0.10 g). mp 207.7–208.9 °C; 1H NMR (400 Hz, CDCl3, 298 K) δ 7.86 (d, J = 7.8 Hz, 2H), 7.85 (d, J = 7.6 Hz, 2H), 7.70 (d, J = 7.3 Hz, 4H), 7.60 (d, J = 8.3 Hz, 4H), 7.58–7.54 (m, 2H), 7.50 (dd, J = 7.8, 1.5 Hz, 2H), 7.45 (dd, J = 7.6, 7.3 Hz, 4H), 7.40 (dd, J = 7.6, 7.6 Hz, 2H), 7.18 (dd, J = 7.6, 7.6 Hz, 2H), 7.10 (d, J = 8.1 Hz, 4H), 6.93 (d, J = 1.5 Hz, 2H), 6.79 (d, J = 7.6 Hz, 2H); 13C NMR (100 Hz, CDCl3, 298 K) δ 195.6, 149.6, 148.2, 144.2, 142.5, 140.6, 137.5, 134.6, 133.6, 132.5, 131.2, 130.7, 129.8, 129.3, 128.6, 128.2, 126.8, 124.0, 121.3, 120.5, 65.7; IR (KBr)  3058, 1653, 1587, 1445, 1399, 1283, 1082, 921, 835, 729, 698 cm–1; HRMS (FAB): calcd. for C31H26N2O2S2Na [M + Na]+, 763.1741; found 763.1744.

Synthesis of MAS

A suspension of mono(arylene thioether) MTE (0.050 g, 0.67 mol) in HCOOH (1 mL) were equipped with a 5 mL round-bottom flask, and then heated at 50 °C. 30 % aq. H2O2 (0.5 mL) was added dropwise and kept at the same temperature for 8 h. After cooling to room temperature, the precipitates were collected by filtration to give MAS as white solids in 98% yield (0.053 g).

mp 266.8–268.6 °C; 1H NMR (400 Hz, CDCl3, 298 K) δ 7.94 (d, J = 8.0 Hz, 2H), 7.88 (dd, J = 8.0, 1.4 Hz, 2H), 7.85 (d, J = 7.8 Hz, 2H), 7.81 (d, J = 8.5 Hz, 4H), 7.74 (d, J = 8.5 Hz, 4H), 7.66 (d, J = 7.1 Hz, 4H), 7.55–7.51 (m, 2H), 7.40 (dd, J = 7.1, 7.2 Hz, 4H), 7.38 (dd, J = 7.8, 7.8 Hz, 2H), 7.29 (d, J = 1.4 Hz, 2H), 7.14 (dd, J = 7.8, 7.8 Hz, 2H), 6.61 (d, J = 7.8 Hz, 2H); 13C NMR (100 Hz, CDCl3, 298 K) δ 195.1, 148.4, 148.2, 147.4, 144.5, 141.6, 139.8, 1139.5, 136.3, 133.2, 130.5, 130.1, 128.9, 128.8, 128.6, 127.4, 124.1, 123.3, 121.5, 121.3, 65.8; IR (KBr)  3056, 2963, 1664, 1598, 1446, 1397, 1317, 1274, 1143, 1092, 925, 805, 754, 697, 667, 611 cm–1; HRMS (FAB): calcd. for C31H26N2O2S2Na [M + Na]+, 827.1538; found 827.1538.

UV-vis spectra of MTE and MAS.

Figure S1. UV-vis spectra of MTE and MAS (298 K, 0.1 mM, CHCl3).

NMR and FT-IR spectar of Poly(arylene sulfone)s (PAS)s.

Figure S2. 1H NMR spectrum (400 MHz, CDCl3, 298 K) (top) and IR spectrum (KBr) (bottom) of PAS1.

Figure S3. 1H NMR spectrum (400 MHz, CDCl3, 298 K) (top) and IR spectrum (KBr) (bottom) of PAS2

.

Figure S4. 1H NMR spectrum (400 MHz, CDCl3, 298 K) (top) and IR spectrum (KBr) (bottom) of PAS3

Figure S5. 1H NMR spectrum (400 MHz, CDCl3, 298 K) (top) and IR spectrum (KBr) (bottom) of PAS4

Figure S6. 1H NMR spectrum (400 MHz, CDCl3, 298 K) (top) and IR spectrum (KBr) (bottom) of PAS5

Figure S7. 1H NMR spectrum (400 MHz, CDCl3, 298 K) (top) and IR spectrum (KBr) (bottom) of PAS6