Double-decker-shaped Silsesquioxane Having

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1 Supporting Information Hydrosilylation Polymerization of Double-decker-shaped Silsesquioxane Having Hydrosilane with Diynes Makoto Seino, Teruaki Hayakawa, Yoshihito Ishida, and Masa-aki Kakimoto* Department of Organic and Polymeric Materials, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo , Japan Kenichi Watanabe and Hisao Oikawa Goi Research Center, Chisso Petrochemical Corporation, 5-1 Goi-Kaigan, Ichihara, Chiba , Japan *Corresponding author Tel: Fax: Materials. Platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(dvs)) 0.1 M solution in xylene was purchased from Aldrich. 1,4-Bis(phenylethynyl)benzene (BPEB) and 9,10-bis(phenylethynyl)anthracene (BPEA) were purified by recrystallization. Toluene and THF were distilled with sodium. Other solvents and reagents were used without further purification. 1

2 Measurements. 1 H, 13 C and 29 Si NMR spectra were recorded in CDCl 3 on a JEOL JNM-AL 300 spectrometer. IR spectra were recorded on a JASCO FT/IR-460 Plus spectrophotometer. Molecular weights were determined by gel permeation chromatography (GPC) with polystyrene calibration using a Shodex GPC-101 with two Shodex LF-804 columns in THF as an eluent. MALDI-TOF MASS spectra were taken on a Simadzu AXIMA-CFA mass spectrometer. The sample solution was prepared in THF, and dithranol and sodium trifluoroacetate were used matrix. The measurement was done in linear mode. Mass value was calibrated by the two-point method with insulin B plus H + at and R-cyanohydroxycinnamic acid dimer plus H + at Differential scanning calorimetry (DSC) was measured with a Seiko DSC 6200 at a heating rate of 10 o C/min under nitrogen. Thermogravimetric analysis (TGA) was carried out with a Seiko TGA 6200 at a heating rate of 10 o C/min under nitrogen. DDSQ. In a 300 ml flask, phenyltrimethoxysilane (242 mmol, 48.0 g), sodium hydroxide (160 mmol, 6.4 g), water (278 mmol, 5.0 g) and 2-propyl alcohol (240 ml) were placed under nitrogen. The mixture was stirred for 4 h with refluxing, and then left at room temperature for a day. The precipitate was filtered and washed once with 2-propyl alcohol, and dried in vacuum at 70 o C for 5 h. To a 300 ml flask are added the precipitate (11.6 g), triethylamine (30 mmol, 3.0 g) and THF (100 ml) under nitrogen. After methyldichlorosilane (30 mmol, 3.4 g) was added dropwise, the mixture was stirred at room temperature for 1 h. To dissolve sodium chloride formed and hydrolyze unreacted methyldichlorosilane, water (50 ml) was added, and the organic layer was separated and washed once with 1N hydrochloric acid and once with saturated sodium hydrogencarbonate aqueous solution and further tree times with ion-exchanged water. The organic layer was dried over magnesium sulfate and condensed by evaporator. The residue was washed with methanol and dried in vacuum to give a white solid DDSQ (6.9 g, yield 20 %). 1 H NMR: δ 0.36 (d, 6H, SiCH 3, J = 1.5 Hz), 4.97 (q, 2H, SiH, J = 1.5 Hz), (m, 40H, Ph). 13 C NMR: δ 0.61, , , , , , , , , , , , , , Si NMR: δ , , , , IR (KBr, cm -1 ): 3073, 3052, 3027, 2967, 2174, 1963, 1892, 1823, 1774, 1595, 1490, 1431, 1263, 2

3 1132, 1029, 998, 904, 894, 771, 730, 717, 698. MALDI-TOF MS (m/e): (C 50 H 48 Si 10 O 14 Na, [M+Na] + =1176.1). Model reaction. To a 20 ml Schlenk flask were added DDSQ (1.154 g, 1 mmol), diphenylacetylene (0.356 g, 2 mmol), and toluene (2 ml) under Argon. Pt(dvs) (20 µl, 0.2 mol%) was added, and the mixture was stirred at 100 o C for 24 h. The products were isolated by preparative GPC. Removal of the solvent gave a white solid 1 (1.111 g, yield 74 %). 1 H NMR: δ 0.37 (s, 6H, SiCH 3 ), (m, 2H, PhCH=C), (m, 60H, Ph). 13 C NMR: δ -1.22, , , , , , , , , , , , , , , , , , , , , , , Si NMR: δ , , , , IR (KBr, cm -1 ): 3073, 3052, 3025, 1595, 1492, 1431, 1262, 1131, 1029, 998, 963, 697. MALDI-TOF MS (m/e): (C 78 H 68 Si 10 O 14 Na, [M+Na] + =1532.2). Polymerization. A typical procedure was as follows (P1 in Table 1). To a 20 ml Schlenk flask were added DDSQ (1.154 g, 1 mmol), 1,4-bis(phenylethynyl)benzene (0.278 g, 1 mmol), and toluene (2 ml) under Argon. Pt(dvs) (20 µl, 0.2 mol%) was added, and the mixture was stirred at 100 o C for 24 h. After reprecipitation from toluene into methanol, the precipitate was collected and dried in vacuum to give a white solid P1 (1.388 g, yield 97 %). GPC: M w /M n = 118,000/29,100. DSC: T g = 153 o C. TGA: T d = 518 o C. 1 H NMR: δ (m, 6H, SiCH 3 ), (m, 56H, CH=C, Ph and phenylene). 13 C NMR: δ -1.46, -1.21, -1.13, , (m), , , , , , , , , (m), (m), , , , , , , , , , , , , Si NMR: δ to (m), to (m), to (m). IR (KBr, cm -1 ): 3073, 3051, 3026, 1595, 1492, 1431, 1261, 1132, 1080, 1028, 998, 965, 729, 696. P2 and P3 were prepared similarly (for polymerization condition, see Table 1). P2 (white solid, g, yield 97 %). GPC: M w /M n = 42,400/14,600. DSC: T g = 156 o C. TGA: T d = 489 o C. P2 gave resemble analytical data to P1. P3 (yellow solid, g, yield 90 %). GPC: M w /M n = 57,700/11,900. 3

4 TGA: T d = 301 o C. 1 H NMR: δ (m, 6H, SiCH 3 ), (m, 60H, CH=C, Ph and anthracene). 13 C NMR: δ -3.82, -2.87, -2.40, -1.75, -1.41, -0.64, -0.47, 0.67, 2.57, , , (m), , , , , , (br), (br), (m), (m), , , , , Si NMR: δ , , , IR (KBr, cm -1 ): 3073, 3052, 3027, 1595, 1491, 1431, 1262, 1132, 1028, 998, 797, 766, 728,

5 Figure 1. 1 H (a), 13 C (b), and 29 Si (c) NMR spectra of DDSQ. 5

6 Figure 2. 1 H (a), 13 C (b), and 29 Si (c) NMR spectra of 1. 6

7 Figure 3. 1 H (a), 13 C (b), and 29 Si (c) NMR spectra of P1. 7

8 Figure 4. MALDI TOF MS spectra of DDSQ (a) and 1 (b). 8