Supporting Information

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1 Supporting Information Gram-Scale Syntheses and Conductivities of [10]Cycloparaphenylene and Its Tetraalkoxy Derivatives Eiichi Kayahara, Liansheng Sun, Hiroaki Onishi, Katsuaki Suzuki, Tatsuya Fukushima, Ayaka Sawada, Hironori Kaji,* and Shigeru Yamago* Institute for Chemical Research, Kyoto University, Uji, Kyoto , Japan General. All reactions dealing with air- and moisture sensitive compounds were carried out in a dry reaction vessel under nitrogen atmosphere. Gel permeation chromatography (GPC) was performed on JAIGEL 1H, 2H, or 2.5H polystyrene columns (Japan Analytical Industry Co., Ltd.) with CHCl 3 as the eluent. 1 H (400 MHz) and 13 C NMR (100 MHz) spectra were measured for a CDCl 3 or dimethyl sulfoxide (DMSO-d 6) solution of a sample and are reported in parts per million ( ) from internal tetramethylsilane or residual solvent peak. Multiplicities and their descriptions are abbreviated as follows: s = singlet, d = doublet, q = quatet, quin = quintet, sext = sextet, sept = septet, m = multiplet, and br = broad. Electrospray ionization time-of-flight mass (ESI-TOF MS) spectrum was recorded on a spectrometer in the positive or negative mode. A sample was injected as a CH 2Cl 2/methanol or acetonitrile solutions. Matrix-assisted laser-desorption ionization time-of-flight mass (MALDI-TOF MS) spectrum was obtained on a spectrometer in the positive reflection mode and at 20 kv acceleration voltage. Samples were prepared from a THF solution by mixing a sample (1 mg/ml) and dithranol (10 mg/ml) in a 1:1 ratio. UV-vis and emission spectra were measured in CHCl 3 at room temperature. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were measured with a Pt electrode for 1,1,2,2-tetrachloroethane or THF solution of a sample (1 mmol/l) in the presence of an supporting electrolyte (Bu 4NPF 6, 0.1 mol/l) at room temperature under nitrogen atmosphere. The potentials were calibrated with respect to the ferrocene/ferrocenium couple (Fc/Fc+). Materials. Unless otherwise noted, commercially available materials were used without purification. CH 2Cl 2 was distilled successively from P 2O 5 and K 2CO 3 and stored over molecular sieves. Toluene was distilled from CaH 2 and stored over molecular sieves. Water content in solvents were determined by Karl-Fisher water titrater. 4-Bromo-4'-iodobiphenyl 1 and dichloro(1,5-cyclooctadiene)platinum [Pt(cod)Cl 2] 2 was synthesized according to literature procedures. S1

2 Synthesis of 2 Table S1. Synthesis of 2. R Product Yield OBu 2C 90% OHex 2D 78% OOct 2E 81% OEtHex 2F 70% OBn 2G 90% General procedure for the synthesis of 2: 2C. The suspension of 2B (8.00 g, 57.1 mmol), n-butanol (104 ml, 1.14 mol), and BF 3 OEt 2 (15.9 ml, 126 mmol) was heated at 65 C for 12 h. The resulting suspension was filtered and the residue was was washed with methanol to give 2C (12.8 g, 90%) as a yellow solid. 2C: 1 H NMR (CDCl 3, 400 MHz) = 0.97 (t, 6H, J = 7.6 Hz, -CH 3), 1.48 (sext, 4H, J = 8.0 Hz, -CH 2-), 1.83 (quin, 4H, J = 6.8 Hz, -CH 2-), 3.93 (t, 4H, J = 6.8 Hz, -OCH 2-), 5.83 ppm (s, 2H, -CH=C(OBu)-); 13 C NMR (CDCl 3, 100 MHz) = 13.62, 19.06, 30.15, 69.54, , , ppm. The NMR spectra were consistent with literature data. 3 2D: The title compound was prepared from 2B (8.00 g, 57.1 mmol), n-hexanol (143 ml, 1.14 mol), and BF 3 OEt 2 (5.90 ml, 126 mmol) according to the general procedure. Yellow solid (13.8 g, 78% yield). 1 H NMR (CDCl 3, 400 MHz) = 0.90 (t, 6H, J = 7.0 Hz, -CH 3), (m, 12H, -CH 2-), 1.85 (quin, 4H, J = 6.8 Hz, -CH 2-), 3.92 (t, 4H, J = 6.4 Hz, -OCH 2-), 5.83 ppm (s, 2H, -CH=C(OHex)-); 13 C NMR (CDCl 3, 100 MHz) = , 22.48, 25.47, 28.14, 31.37, 69.85, , , ppm. The NMR spectra were consistent with literature data. 3 2E: The title compound was prepared from 2B (5.00 g, 35.7 mmol), n-octanol (113 ml, 710 mmol), and BF 3 OEt 2 (10.0 ml, 78.5 mol) according to the general procedure. Yellow solid (10.5 g, 81% yield). 1 H NMR (CDCl 3, 400 MHz) = 0.88 (t, 6H, J = 7.0 Hz, -CH 3), (m, 20H, -CH 2-), 1.84 (quin, 4H, J = 7.2 Hz, -CH 2-), 3.92 (t, 4H, J = 6.8 Hz, -OCH 2-), 5.83 ppm (s, 2H, -CH=C(OOct)-); 13 C NMR (CDCl 3, 100 MHz) = 14.04, 22.60, 25.80, 28.17, 29.09, 29.16, 31.72, 69.86, , , ppm. The NMR spectra were consistent with literature data. 3 2F: The title compound was prepared from 2B (5.00 g, 35.7 mmol), 2-ethylhexanol (113 ml, 710 mmol), and BF 3 OEt 2 (10.0 ml, 78.5 mmol) according to the general procedure. Yellow solid (9.1 g, 70% yield). 1 H NMR (CDCl 3, 400 MHz) = 0.88 (t, 6H, J = 7.0 Hz, -CH 3), (m, 20H, -CH 2-), 1.84 (quin, 4H, J = 7.2 Hz, -CH 2-), 3.92 (t, 4H, J = 6.8 Hz, -OCH 2-), 5.83 ppm (s, 2H, -CH= S2

3 C(OEtHex)-); 13 C NMR (CDCl 3, 100 MHz) = 14.04, 22.61, 25.80, 28.18, 29.10, 29.16, 31.73, 69.86, , , ppm. The NMR spectra were consistent with literature data. 4 2G: The title compound was prepared from 2B (14.0 g, 100 mmol), benzyl alcohol (104 ml, 1.00 mol), and BF 3 OEt 2 (13.8 ml, 110 mmol) according to the general procedure. Yellow solid (28.1 g, 90% yield). 1 H NMR (CDCl 3, 400 MHz) = 5.05 (s, 4H, -OCH 2-), 5.92 (s, 2H, -CH=C(OBn)-), ppm (m, 10H, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 71.36, , , , , , , ppm. HRMS (EI) m/z: Calcd for C 20H 16O 2 [M] +, , found ; IR (KBr) 728, 860, 959, 1003, 1072, 1239, 1357, 1403, 1458, 1607, 2875, 2952; mp o C. Synthesis of 3a. Table S2. Synthesis of 3a. Substrate Product Yield (%) 2A 3aA 42 2C 3aC 88 2D 3aD 82 2E 3aE 68 2F 3aF 85 2G 3aG 85 Synthesis of 3aA. To a solution of 4-bromo-4'-iodobiphenyl (28.8 g, 80.0 mmol) in THF (400 ml) was slowly added BuLi (51.3 ml, 1.56 M in hexane, 80.0 mmol) at -78 C using a syringe. After stirring for 1 h at same temperature, the resulting 4-bromo-4 -lithiobiphenyl was added to a solution of 1,4-benzoquinone (2.16 g, 20.0 mmol) in THF (200 ml) through a cannula at -78 C. After stirring for 2 h at same temperature, the reaction mixture was quenched with saturated aqueous NH 4Cl solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2SO 4, filtered and concentrated to give a crude mixture. The residue was purified by silica gel chromatography (hexane/ethyl acetate = 1:1) to give the diol (5.06 g). Although this material contained a minor amount of uncharacterized side products, this product could be used for the subsequent reaction. To a solution of the diol (5.06 g, 8.81 mmol) and imidazole (2.42 g, 35.3 mmol) in DMF (30 ml) was slowly added triethylsilyl chloride (TESCl, 4.44 ml, 26.5 S3

4 mmol) at room temperature. After stirring for 12 h at same temperature, the resulting suspension was added to ice-water, then extracted with ether. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2SO 4, filtered and concentrated under reduced pressure to give a crude mixture. Purification by silica gel chromatography (hexane/ethyl acetate = 95:5) afforded 3aA in 42% yield (6.74 g, 2 steps from 2A) as a colorless solid. 3aA: 1 H NMR (CDCl 3, 400 MHz) 0.63 (q, 12H, J = 8.0 Hz, -SiEt 3), 0.95 (t, 18H, J = 8.0 Hz, -SiEt 3), 6.04 (s, 4H, -CH=CH-), 5.97 (s, 4H, -CH=CH-), 7.42 (d, 4H, J = 8.8 Hz, -Ar), 7.44 (d, 4H, J = 8.8 Hz, -Ar), 7.47 (d, 4H, J = 8.4 Hz, -Ar), 7.54 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) 6.49, 7.05, 71.34, , , , , , , , , ppm; HRMS (FAB-MS) m/z: Calcd for C 42H 50Br 2O 2Si 2 [M] +, , found ; IR (KBr) 728, 860, 959, 1003, 1072, 1239, 1357, 1403, 1458, 1607, 2875, 2952 cm -1 ; mp o C. General procedure for the syntheses of 3aC-G: 3aC. To a solution of 4-bromo-4'-iodobiphenyl (22.8 g, 63.4 mmol) in THF (500 ml) was slowly added BuLi (40.7 ml, 1.50 M in hexane, 63.4 mmol) at -78 C using a syringe. After stirring for 1 h at same temperature, the resulting 4-bromo-4 - lithiobiphenyl was added to a solution of 2C (4.00 g, 15.9 mmol) in THF (400 ml) through a cannula at -78 C. After stirring for 1 h at same temperature, the resulting solution was warmed to room temperature over 2 h. Treaction mixture was quenched with saturated aqueous NH 4Cl solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2SO 4, filtered and concentrated under reduced pressure to give a crude mixture. To remove the protonated 4-bromobiphenyl derived from starting material, the crude product was passed through a silica gel (hexane/ethyl acetate = 1:1) to give the diol. Although this material contained a minor amount of uncharacterized side products, this product could be used for the subsequent reaction. To a solution of the diol and imidazole (5.40 g, 79.3 mmol) in DMF (80 ml) was slowly added triethylsilyl chloride (TESCl, 7.96 ml, 47.6 mmol) at room temperature. After stirring for 12 h at same temperature, the resulting suspension was added to ice-water, then extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2SO 4, filtered and concentrated under reduced pressure to give a crude mixture. Purification by silica gel chromatography (hexane/ethyl acetate = 95:5) afforded 3aC in 88% yield (13.2 g, 2 steps from 2C) as a colorless solid. 3aC: 1 H NMR (CDCl 3, 400 MHz) (m, 12H, -SiEt 3), 0.84 (t, 6H, J = 7.6 Hz, -CH 3), 0.97 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 4H, -CH 2-), (m, 4H, -CH 2-), (dt, 2H, J = 9.2, 2.4 Hz -OCH 2-), (dt, 2H, J = 9.2, 2.4 Hz -OCH 2-), 4.86 (s, 2H, -CH=C(OBu)-), 7.45 (s, 8H, -Ar), 7.46 (d, 4H, J = 8.8 Hz, -Ar), 7.54 (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) 6.32, 7.20, 13.74, 19.21, 30.88, 66.72, 75.30, , , , , , , , , , ppm; HRMS (ESI-MS) m/z: Calcd for C 50H 66Br 2O 4Si 2Na [M + Na] +, , found ; 729, 818, 1003, 1063, 1152, 1481, 1647, 2874, 2953 cm -1 ; mp o C. S4

5 3aD: The title compound was prepared from 2D (7.50 g, 25.3 mmol), 4-bromo-4'-iodobiphenyl (34.9 g, 97.3 mmol), imidazole (8.28g, 122 mmol), and TESCl (12.2 ml, 73.0 mmol) according to the general procedure. Yellow solid (20.1 g, 82% yield). 1 H NMR (CDCl 3, 400 MHz) (m, 12H, -SiEt 3), 0.81 (t, 6H, J = 7.6 Hz, -CH 3), 0.97 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 4H, -CH 2-), (m, 4H, -CH 2-), (dt, 2H, J = 8.8, 2.4 Hz -OCH 2-), (dt, 2H, J = 8.8, 2.5 Hz -OCH 2-), 4.85 (s, 2H, -CH=C(OHex)-), 7.45 (s, 8H, -Ar), 7.46 (d, 4H, J = 8.8 Hz, -Ar), 7.53 (d, 4H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.31, 7.21, 13.94, 22.53, 25.70, 28.78, 31.43, 66.99, 75.29, , , , , , , , , , ppm; IR (KBr) 729, 816, 1003, 1074, 1152, 1481, 1647, 2874, 2953 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 54H 70Br 2O 6Si 2Na [M + Na] +, , found ; mp o C. 3aE: The title compound was prepared from 2E (6.00 g, 16.5 mmol), 4-bromo-4'-iodobiphenyl (23.6 g, 65.8 mmol), imidazole (5.51 g, 81.0 mmol), and TESCl (8.27 ml, 49.4 mmol) according to the general procedure. Yellow solid (12.3 g, 68% yield). 1 H NMR (CDCl 3, 400 MHz) (m, 12H, -SiEt), 0.83 (t, 6H, J = 6.8 Hz, -CH 3), 0.97 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 4H, -CH 2-), (m, 4H, -CH 2-), (m, 4H, -OCH 2-), 4.85 (s, 2H, -CH=C(Ooct)-), 7.45 (s, 8H, -Ar), 7.46 (d, 4H, J = 8.0 Hz, -Ar), 7.54 (d, 4H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.31, 7.21, 14.03, 22.61, 26.03, 28.82, 29.19, 29.21, 31.73, 66.99, 75.29, , , , , , , , , , ppm; IR (KBr) 729, 816, 1003, 1074, 1149, 1481, 1645, 2857, 2953 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 58H 78Br 2O 6Si 2Na [M + Na] +, , found ; mp o C. 3aF: The title compound was prepared from 2F (5.90 g, 13.8 mmol), 4-bromo-4'-iodobiphenyl (23.2 g, 64.7 mmol), imidazole (5.51 g, 81.0 mmol), and TESCl (8.13 ml, 48.6 mmol) according to the general procedure. Yellow solid (14.5 g, 85% yield). 1 H NMR (CDCl 3, 400 MHz) (m, 12H, -SiEt 3), (m, 12H, -CH 3), 0.97 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 16H, -CH 2-), (m, 2H, -CH-), (m, 2H, -OCH 2-), (m, 2H, -OCH 2-), 4.81 (s, 1H, - CH=C(OEtHex)-), 4.81 (s, 1H, -CH=C(OEtHex)-), (m, 8H, -Ar), 7.49 (d, 4H, J = 7.6 Hz, - Ar), 7.53 (d, 4H, J = 7.6 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.44, 7.21, 10.91, 11.15, 14.03, 14.06, 22.94, 23.01, 23.78, 24.06, 28.91, 29.12, 30.41, 30.84, 39.15, 39.27, 68.96, 69.19, 75.27, , , , , , , , , , , , , ppm; IR (KBr) 727, 804, 1003, 1074, 1149, 1481, 1647, 2873, 2957 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 58H 78Br 2O 6Si 2Na [M + Na] +, , found ; mp o C. 3aG: The title compound was prepared from 3G (6.40 g, 20.0 mmol), 4-bromo-4'-iodobiphenyl (29.0 g, 81.0 mmol), imidazole (6.87 g, 101 mmol), and TESCl (11.8 ml, 70.4 mmol) according to the general procedure. Yellow solid (17.2 g, 85% yield). 1 H NMR (CDCl 3, 400 MHz): = 0.62 (q, 12H, J = 8.0 Hz, -SiEt 3), 0.93 (t, 18H, J = 7.6 Hz, -SiEt 3), 4.81 (ABq, 4H, Δδ AB = 0.11, J AB = 12.0 Hz, - OCH 2-), 4.91 (s, 2H, -CH=C(OBn)-), (m, 4H, -Ph), (m, 6H, -Ph), 7.36 (d, 4H, J S5

6 = 8.0 Hz, -Ar), 7.40 (d, 4H, J = 8.0 Hz, -Ar), 7.46 (d, 4H, J = 8.8 Hz, -Ar), 7.55 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.38, 7.16, 68.89, 75.17, , , , , , , , , , , , , , , , ppm; IR (KBr) 722, 809, 860, 956, 1005, , 1478, 1645, 2856, 2955 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 56H 62Br 2O 4Si 2Na [M + Na] +, , found , o C. Synthesis of 3b Table S3. Synthesis of 3b. Substrate Product Yield (%) 3aA 3bA 91 3aC 3bC 93 3aD 3bD 97 3aE 3bE 93 3aF 3bF 95 3aG 3bG 82 General procedure for the syntheses of 3b: 3bA. To a solution of 3aA (12.0 g, 15.0 mmol) in THF (100 ml) was added BuLi (24.0 ml, 1.57 M in hexane, 37.5 mmol) through a syringe at -78 ºC over 10 min. After stirring for 1 h at this temperature, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2- dioxaborolane ( i PrOBpin, 9.10 ml, 45.0 mmol) was slowly added at -78 o C, and the resulting mixture was slowly warmed to room temperature. After stirring for 1 h at this temperature, and the resulting mixture was slowly warmed to room temperature over 2 h. After stirring for 3 h at this temperature, the reaction mixture was quenched with saturated aqueous NH 4Cl solution, and was extracted with ethyl acetate. The combined organic layer was washed with saturated aqueous NaCl solution, dried over Na 2SO 4, filtered and concentrated under reduced pressure to give a crude mixture. The crude mixture was washed with MeOH to give 3bA (12.2 g, 91%) as a colorless solid. 1 H NMR (CDCl 3, 400 MHz) = 0.63 (q, 12H, J = 8.0 Hz, SiMe 2), 0.95 (t, 18H, J = 8.0 Hz, SiEt 3), 1.36 (s, 24H, -Bpin), 6.04 (s, 4H, -CH=CH-), 7.43 (d, 4H, J = 8.4 Hz, -Ar), 7.54 (d, 4H, J = 8.4 Hz, -Ar), 7.60 (d, 4H, J = 8.4 Hz, -Ar), 7.86 (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.49, 7.05, 24.87, 71.36, S6

7 83.78, , , , , , , , , , ppm; HRMS (FAB-MS) m/z: Calcd for C 54H 74B 2O 6Si 2 [M] +, , found ; IR (KBr) 648, 725, 961, 1076, 1348, 1458, 1709, 2875, 2954 cm -1 ; mp o C. 3bC: The title compound was prepared from 3aC (8.00 g, 8.45 mmol), BuLi (13.7 ml, 1.54 M in hexane, 21.1 mmol), and i PrOBpin (5.17 ml, 25.3 mmol) according to the general procedure. Colorless solid (8.20 g, 93% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 12H, -SiEt 3), 0.83 (t, 6H, J = 7.2 Hz, -CH 3), 0.97 (t, 18H, J = 7.6 Hz, -SiEt 3), (m, 4H, -CH 2-), (m, 4H, -CH 2-), (m, 2H, -OCH 2-), (m, 2H, -OCH 2-), 4.86 (s, 2H, -CH=C(OBu)-), 7.46 (d, 4H, J = 8.4 Hz, -Ar), 7.52 (d, 4H, J = 8.4 Hz, -Ar), 7.61 (d, 4H, J = 8.4 Hz, -Ar), 7.86 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.24, 7.21, 13.74, 19.21, 24.89, 30.90, 66.70, 75.36, 83.77, , , , , , , , , , ppm; HRMS (ESI-TOF) m/z: C 62H 90B 2O 8Si 2Cs [M + Cs] +, , found ; IR (KBr) 658, 739, 821, 1094, 1148, 1362, 1611, 1647, 2874, 2957 cm -1 ; mp o C. 3bD: The title compound was prepared from 3aD (18.0 g, 17.9 mmol), BuLi (1.55 M, 28.9 ml, 44.9 mmol), and i PrOBpin (10.9 ml, 53.8 mmol) according to the general procedure. Colorless solid (19.2 g, 97% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 12H, -SiEt 3), (m, 6H, -CH 3), 0.96 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 12H, -CH 2-), 1.36 (s, 18H, -Bpin), (m, 4H, - CH 2-), (m, 4H, OCH 2-), 4.86 (s, 2H, -CH=C(OHex)-), 7.46 (d, 4H, J = 8.8 Hz, -Ar), 7.52 (d, 4H, J = 8.8 Hz, -Ar), 7.61 (d, 4H, J = 8.4 Hz, -Ar), 7.86 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.32, 7.22, 13.94, 22.53, 24.88, 25.70, 28.79, 31.44, 66.95, 75.35, 83.76, , , , , , , , , , ppm; IR (KBr) 658, 735, 822, 1092, 1148, 1362, 1611, 1647, 2873, 2955 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 66H 98B 2O 8Si 2Cs [M + Cs] +, , found ; mp o C. 3bE: The title compound was prepared from 3aE (10.0 g, 9.44 mmol), BuLi (1.55 M, ml, 23.7 mmol), and i PrOBpin (5.78 ml, 28.3 mmol) according to the general procedure. Colorless solid (10.1 g, 93% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 12H, -SiEt 3), 0.83 (t, 6H, J = 6.8 Hz, - CH 3), 0.97 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 20H, -CH 2-), 1.36 (s, 18H, -Bpin), (m, 4H, -CH 2-), (m, 2H, -OCH 2-), (m, 2H, -OCH 2-), 4.86 (s, 2H, -CH=C(OOct)-), 7.46 (d, 4H, J = 8.8 Hz, -Ar), 7.51 (d, 4H, J = 8.4 Hz, -Ar), 7.61 (d, 4H, J = 8.4 Hz, -Ar), 7.86 ppm (d, 4H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.34, 7.22, 14.05, 22.61, 24.87, 26.03, 28.83, 29.18, 29.21, 31.73, 66.96, 75.36, 83.74, , , , , , , , , , ppm; IR (KBr) 658, 741, 822, 1092, 1148, 1362, 1611, 1647, 2874, 2953 cm - 1 ; HRMS (MALDI-TOF) m/z: Calcd for C 70H 106B 2O 8Si 2Cs [M + Cs] +, , found ; mp o C. 3bF: The title compound was prepared from 3aF (13.0 mg, 12.3 mol), BuLi (1.55 M, 19.8 ml, 30.7 mmol), and i PrOBpin (7.51 ml, 36.8 mmol) according to the general procedure. Colorless solid (13.5 S7

8 g, 95% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3 and -CH 3), 0.97 (t, 18H, J = 8.0 Hz, -SiEt 3), (m, 16H, -CH 2-), 1.36 (s, 18H, -Bpin), (m, 2H, -CH-), (m, 2H, -OCH 2-), (m, 2H, -OCH 2-), 4.81 (s, 2H, -CH=C(OEtHex)-), (m, 8H, -Ar), 7.61 (d, 4H, J = 8.0 Hz, -Ar), 7.86 (d, 4H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.44, 7.21, 10.89, 11.14, 14.02, 14.05, 22.94, 23.00, 23.77, 24.04, 24.87, 28.90, 29.11, 30.41, 30.83, 39.15, 39.27, 68.90, 69.16, 75.32, 83.75, , , , , , , , , , , , , ppm; IR (KBr) 658, 721, 822, 1094, 1146, 1362, 1610, 1647, 2876, 2959 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 70H 106B 2O 8Si 2Cs [M + Cs] +, , found ; mp o C. 3bG: The title compound was prepared from 3aG (10.1 g, 10.0 mmol), BuLi (16.1 ml, 1.55 M in hexane, 24.9 mmol), and i PrOBpin (6.20 ml, 30.0 mmol) according to the general procedure. Yellow solid (9.10 g, 82%). 1 H NMR (CDCl 3, 400 MHz) = 0.61 (q, 12H, J = 8.0 Hz, SiEt 3), 0.93 (t, 18H, J = 8.0 Hz, -SiEt 3), 4.82 (ABq, 4H, Δδ AB = 0.12, J AB = 12.4 Hz, -OCH 2-), 4.92 (s, 2H, -CH=C(OBn)-), (m, 4H, -Ph), (m, 6H, -Ph), 7.38 (d, 4H, J = 8.4 Hz, -Ar), 7.47 (d, 4H, J = 8.0 Hz, -Ar), 7.62 (d, 4H, J = 8.0 Hz, -Ar), 7.87 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.38, 7.16, 24.86, 68.88, 75.21, 83.77, , , , , , , , , , , , , , ppm; IR (KBr) 640, 722, 820, 1160, 1352, 1635, 2875, 2955 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 62H 72B 2O 7Si [M] +, , found ; d.p. > 300 o C. S8

9 Synthesis of 4. Table S4. Synthesis of 4. Substrate Product Yield (%) 3bA 4A 68 3bC 4C 51 3bD 4D 48 3bE 4E 44 3bF 4F 39 3bG 4G 57 General procedure for the syntheses of 4: 4A. Suspension of Pt(cod)Cl 2 (0.30 g, 0.80 mmol), 3bA (0.72 g, 0.80 mmol), and K 3PO 4 (0.68 g, 3.2 mmol) in THF (160 ml) was heated at 65 o C for 18 h under a nitrogen atmosphere. To the resulting mixture was added water, and was extracted with CH 2Cl 2. The combined organic layers were washed with brine, dried over Na 2SO 4, filtered through a pad of Celite, and concentrated under reduced pressure to give a crude mixture. The residue was purified by preparative gel permeation chromatography using chloroform as the eluent giving 4A (0.51 g, 68%). In large scale synthesis, the formation of 4A was confirmed by by 1 H NMR, the crude mixture was used to the next step without further purification. See the general procedure of large scale synthesis (Page S9). 1 H NMR (CDCl 3, 400 MHz) = 0.63 (q, 24H, J = 8.0 Hz, -SiEt 3), 0.97 (t, 36H, J = 8.0 Hz, -SiEt 3), 2.54 (brs, 16H, -cod), 5.23 (brs, 8H, -cod), 6.03 (s, 8H, -CH=CH-), 6.88 (d, 8H, J = 8.4 Hz, - Ar), 7.39 (d, 8H, J = 8.4 Hz, -Ar), 7.46 (d, 8H, J = 8.4 Hz, -Ar), 7.53 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.47, 7.06, 29.78, 73.45, , , , , , , , , , , ppm; HRMS (MALDI-TOF) m/z: Calcd for C 100H 124O 4Pt 2Si 4Ag [M + Ag] +, , found ; IR (KBr) 739, 863, 957, 1004, 1057, 1238, 1414, 1458, 2875, 2957 cm -1 ; d.p. > 180 o C. 4C: The title compound was prepared from 3bC (300 mg, mmol), Pt(cod)Cl 2 (108 mg, mmol), and K 3PO 4 (308 mg, 1.44 mmol) according to the general procedure. Yellow solid (160 mg, 51% yield). In large scale synthesis, the formation of 4C was confirmed by by 1 H NMR, the crude mixture was used to the next step without further purification. See the general procedure of large scale synthesis (Page S9). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), 0.77 (t, 6H, J = 8.0 S9

10 Hz, -CH 3), 0.77 (t, 6H, J = 8.0 Hz, -CH 3), 0.94 (t, 36H, J = 8.4 Hz, -SiEt 3), (m, 8H, -CH 2-), (m, 8H, -CH 2-), 2.54 (brs, 16H, -cod), (m, 8H, -OCH 2-), 4.81 (d, 8H, J = 2.8 Hz, -CH=C(OBu)-), 5.19 (brs, 8H, -cod), 7.28 (d, 8H, J = 8.0 Hz, -Ar), 7.32 (d, 8H, J = 8.4 Hz, -Ar), 7.34 (dd, 8H, J = 8.4, 2.8 Hz, -Ar), 7.40 ppm (d, 8H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.30, 7.21, 13.72, 19.15, 29.90, 30.86, 66.55, 75.42, 75.45, , , , , , ,126.35, , , , , , , , , , ppm; IR (KBr) 741, 806, 1003, 1074, 1152, 1238, 1369, 1460, 1647, 2874, 2953 cm -1 ; HRMS (ESI-MS) m/z: Calcd for C 116H 156O 8Pt 2Si 4Na [M + Na] +, , found ; d.p. > 150 o C. 4D: The title compound was prepared from 3bD (300 mg, mmol), Pt(cod)Cl 2 (102 mg, mmol), and K 3PO 4 (290 mg, 1.37 mmol) according to the general procedure. Yellow solid (150 mg, 48% yield). In large scale synthesis, the formation of 4D was confirmed by by 1 H NMR, the crude mixture was used to the next step without further purification. See the general procedure of large scale synthesis (Page S9). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), 0.79 (t, 12H, J = 6.8 Hz, -CH 3), 0.94 (t, 36H, J = 7.6 Hz, -SiEt 3), (m, 24H, -CH 2-), (m, 8H, -CH 2-), 2.57 (brs, 16H, cod), (m, 4H, -OCH 2-), (m, 4H, -OCH 2-), 4.80 (s, 4H, - CH=C(OHex)-), 5.21 (brs, 8H, cod), 7.27 (d, 8H, J = 8.4 Hz, -Ar), 7.31 (d, 8H, J = 8.4 Hz, -Ar), 7.34 (d, 8H, J = 8.4 Hz, -Ar), 7.39 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.32, 7.22, 13.95, 22.46, 25.63, 28.75, 29.93, 31.45, 66.87, 75.43, , , , , , , , , , , ppm; IR (KBr) 741, 806, 1003, 1072, 1152, 1238, 1369, 1460, 1647, 2874, 2951 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 124H 172O 8Pt 2Si 4Na [M + Na] +, , found ; d.p. > 160 o C. 4E: The title compound was prepared from 3bE (220 mg, mmol), Pt(cod)Cl 2 (71.4 mg, mmol), and K 3PO 4 (202 mg, mmol) according to the general procedure. Yellow solid (101 mg, 44% yield). In large scale synthesis, the formation of 4E was confirmed by by 1 H NMR, the crude mixture was used to the next step without further purification. See the general procedure of large scale synthesis (Page S9). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), 0.79 (t, 12H, J = 6.8 Hz, -CH 3), 0.94 (t, 36H, J = 7.6 Hz, -SiEt 3), (m, 48H, -CH 2-), 2.57 (brs, 16H, cod), (m, 8H, -OCH 2-), 4.80 (s, 4H, -CH=C(OOct)-), 5.21 (brs, 8H, cod), 7.29 (d, 8H, J = 8.4 Hz, -Ar), 7.31 (d, 8H, J = 8.4 Hz, -Ar), 7.34 (d, 8H, J = 8.4 Hz, -Ar), 7.39 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.32, 7.22, 14.04, 22.59, 25.96, 28.80, 29.12, 29.22, 29.91, 31.73, 66.87, 75.42, , , , , , , , , , , ppm; IR (KBr) 741, 806, 1001, 1072, 1150, 1238, 1368, 1460, 1647, 2874, 2951 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 132H 188O 8Pt 2Si 4Na [M + Na] +, , found ; d.p. > 160 o C. 4F: The title compound was prepared from 2bF (200 mg, mol), Pt(cod)Cl 2 (64.9 mg, mmol), and K 3PO 4 (184 mg, mmol) according to the general procedure. Yellow solid (81 mg, 39% yield). In large scale synthesis, the formation of 4F was confirmed by by 1 H NMR, the crude S10

11 mixture was used to the next step without further purification. See the general procedure of large scale synthesis (Page S9). 1 H NMR (CDCl 3, 400 MHz) = (m, 48H, -SiEt 3, -CH 3), 0.94 (t, 36H, J = 7.6 Hz, -SiEt 3), (m, 32H, -CH 2-), (m, 4H, -CH-), 2.57 (brs, 16H, cod), (m, 8H, -OCH 2-), 4.76 (s, 4H, -CH=C(OEtHex)-), 5.22 (brs, 8H, cod), 7.27 (d, 8H, J = 7.6 Hz, - Ar), 7.31 (d, 8H, J = 8.4 Hz, -Ar), 7.39 ppm (d, 16H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.32, 7.22, 14.04, 22.59, 25.96, 28.80, 29.12, 29.22, 29.91, 31.73, 66.87, 75.42, , , , , , , , , , , ppm; IR (KBr) 741, 804, 1003, 1072, 1150, 1240, 1369, 1464, 1645, 2874, 2955 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 132H 188O 8Pt 2Si 4Na [M + Na] +, , found ; d.p. > 160 o C. 4G: The title compound was prepared from 2bG (400 mg, mmol), Pt(cod)Cl 2 (134 mg, mmol), and K 3PO 4 (303 mg, 1.43 mmol) according to the general procedure. Yellow solid (238 mg, 57% yield). In large scale synthesis, the formation of 4G was confirmed by by 1 H NMR, the crude mixture was used to the next step without further purification. See the general procedure of large scale synthesis (Page S9). 1 H NMR (CDCl 3, 400 MHz) = 0.58 (q, 12H, J = 8.0 Hz, -SiEt 3), 0.60 (q, 12H, J = 8.0 Hz, -SiEt 3), 0.90 (t, 36H, J = 8.0 Hz, -SiEt 3), 2.57 (brs, 16H, cod), 4.71 (ABq, 4H, Δδ AB = 0.11, J AB = 12.4 Hz, -OCH 2-), 5.22 (brs, 8H, cod), (m, 8H, -Ph), (m, 12H, -Ph), 7.22 (dd, 8H, J = 7.6, 4.8 Hz, -Ar), 7.30 (d, 8H, J = 8.4 Hz, -Ar), 7.35 (d, 8H, J = 8.8 Hz, -Ar), 7.36 ppm (d, 8H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.36, 7.17, 29.68, 29.94, 30.20, 68.74, 75.25, 75.28, , , , , , , , , , , , , , , , , , , , ppm; IR (KBr) 722, 818, 860, 958, 1005, 1070, 1185, 1237, 1407, 1460, 2877, 2952 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 128H 148O 8Pt 2Si 4 [M] +, , found ; d.p. > 200 o C. S11

12 Synthesis of 5c. Table S5. Synthesis of 5c. Substrate Product Yield 4A 5cA 73 4C 5cC 80 4D 5cD 72 4E 5cE 69 4F 5cF 69 4G 5cG 82 General procedure for the syntheses of 5c. 5cA: A solution of 4A (473 mg, mmol) and PPh 3 (328 mg, 1.25 mmol) in toluene (50 ml) was heated at 105 C for 18 h under nitrogen atmosphere. The resulting suspension was filtered, and the filtrate was concentrated under reduced pressure to give a crude mixture. The residue was purified by silica gel chromatography (hexane/ch 2Cl 2 = 5:1) to give 5cA (246 mg, 73%) as a colorless solid. 1 H NMR (CDCl 3, 400 MHz) = 0.65 (q, 24H, J = 7.6 Hz, - SiEt 3), 0.98 (t, 36H, J = 7.6 Hz, -SiEt 3), 6.34 (s, 8H, -CH=CH-), 7.00 (d, 8H, J = 8.4 Hz, -Ar), 7.11 ppm (d, 8H, J = 8.8 Hz, -Ar), 7.32 (d, 8H, J = 8.4 Hz, -Ar), 7.46 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.47, 7.04, 72.47, , , , , , , , , ppm; HRMS (MALDI-TOF) m/z: Calcd for C 79H 87O 3Si 3 [M] +, , found ; IR (KBr) 713, 816, 863, 965, 1024, 1069, 1238, 1360, 1445, 1495, 2775, 2910 cm - 1 ; mp o C. 5cC: The title compound was prepared from 4C (100 mg, mmol) and PPh 3 (57.2 mg, mmol) according to the general procedure. Yellow solid (59 mg, 80% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), 0.99 (t, 12H, J = 7.2 Hz, -CH 3), 1.00 (t, 36H, J = 8.0 Hz, -SiEt 3), (m, 8H, -CH 2-), (m, 8H, -CH 2-), (m, 8H, -OCH 2-), 5.13 (s, 2H, - CH=C(OBu)-), 5.17 (s, 2H, - CH=C(OBu)-), 6.94 (d, 4H, J = 8.4 Hz, -Ar), 6.98 (d, 4H, J = 8.4 Hz, - Ar), 7.08 (d, 8H, J = 8.4 Hz, -Ar), 7.33 (d, 8H, J = 8.4 Hz, -Ar), 7.46 ppm (d, 8H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.30, 7.21, 13.72, 19.15, 29.90, 30.86, 66.55, 75.42, 75.45, , , , , , , , , , , , , , S12

13 144.84, , , ppm; IR (KBr) 741, 800, 1005, 1094, 1238, 1491, 1638, 2874, 2957 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 94H 117O 7Si 3 (M) +, , found ; mp o C. 5cD: The title compound was prepared from 4D (85.0 mg, mmol) and PPh 3 (48.6 mg, mmol) according to the general procedure. Yellow solid (45 mg, 72% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), (m, 12H, -CH 3), 1.00 (t, 36H, J = 8.0 Hz, -SiEt 3), (m, 16H, -CH 2-), (m, 8H, -CH 2-), (m, 8H, -CH 2-), (m, 8H, - OCH 2-), 5.13 (s, 2H, -CH=C(OHex)-), 5.17 (s, 2H, - CH=C(OHex)-), 6.96 (d, 4H, J = 8.4 Hz, -Ar), 6.99 (d, 4H, J = 8.0 Hz, -Ar), 7.08 (d, 8H, J = 8.0 Hz, -Ar), 7.33 (d, 8H, J = 8.0 Hz, -Ar), 7.47 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.46, 7.25, 14.10, 22.66, 26.01, 29.06, 31.67, 67.45, 75.08, 75.15, , , , , , , , , , , , , , ppm; IR (KBr) 741, 810, 1005, 1096, 1238, 1487, 1634, 2874, 2953 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 102H 133O 7Si 3 (M) +, , found ; mp o C 5cE: The title compound was prepared from 4E (91.2 mg, mmol) and PPh 3 (106 mg, mmol) according to the general procedure. Yellow solid (47 mg, 69% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), (m, 12H, -CH 3), 1.01 (t, 36H, J = 8.0 Hz, -SiEt 3), (m, 40H, -CH 2-), (m, 8H, -CH 2-), (m, 8H, -OCH 2-), 5.13 (s, 2H, - CH=C(OOct)-), 5.17 (s, 2H, -CH=C(OOct)-), 6.96 (d, 4H, J = 8.4 Hz, -Ar), 6.99 (d, 4H, J = 8.4 Hz, - Ar), 7.08 (d, 8H, J = 8.4 Hz, -Ar), 7.33 (d, 8H, J = 8.4 Hz, -Ar), 7.47 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 6.42, 7.21, 14.06, 22.63, 25.97, 29.04, 31.63, 67.42, 75.04, 75.11, , , , , , , , , , , , , , ppm; IR (KBr) 741, 812, 1003, 1086, 1236, 1487, 1635, 2874, 2955 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 110H 149O 7Si 3 [M] +, , found ; mp o C. 5cF: The title compound was prepared from 4F (50.0 mg, mmol) and PPh 3 (27.2 mg, mmol) according to the general procedure. Yellow solid (26 mg, 69% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -SiEt 3), (m, 24H, -CH 3), 1.00 (t, 36H, J = 8.0 Hz, -SiEt 3), (m, 28H, -CH 2-), (m, 2H, -CH-), (m, 2H, -CH-), (m, 8H, - OCH 2-), 5.10 (s, 2H, -CH=C(OEtHex)-), 5.11 (s, 2H, -CH=C(OEtHex)-), (m, 8H, -Ar), 7.09 (d, 8H, J = 8.4 Hz, -Ar), 7.34 (d, 8H, J = 8.4 Hz, -Ar), 7.47 ppm (d, 8H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.44, 7.20, 10.84, 11.28, 14.16, 14.16, 23.06, 23.14, 24.04, 28.98, 29.25, 30.37, 30.93, 39.16, 39.36, 69.67, 69.70, 75.05, 75.05, , , , , , , , , , , , , ppm; IR (KBr) 741, 808, 1005, 1092, 1238, 1487, 1634, 2874, 2957 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 110H 149O 7Si 3 [M] +, , found ; mp o C. S13

14 5cG: The title compound was prepared from 4G (232 mg, mmol) and PPh 3 (131 mg, mmol) according to the general procedure. Yellow solid (140 mg, 82% yield). 1 H NMR (CDCl 3, 400 MHz): = (m, 24H, -SiEt 3), 0.94 (t, 36H, J = 8.0 Hz, -SiEt 3), 4.98 (s, 8H, -OCH 2Ph), 5.24 (s, 2H, -CH=C(OBn)-), 5.25 (s, 2H, -CH=C(OBn)-), 6.91 (dd, 4H, J = 8.0, 2.8 Hz, -Ar), 7.05 (d, 8H, J = 8.4 Hz, -Ar), 7.34 (d, 8H, J = 8.4 Hz, -Ar), (m, 12H, -Ar), (m, 8H, -Ar), 7.49 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 6.38, 7.17, 69.47, 75.03, 75.05, 77.20, , , , , , , , , , , , , , , , ppm; IR (KBr) 741, 786, 826, 1021, 1250, 1512, 1653, 2855, 2925 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 106H 109O 7Si 3 [M] +, , found ; mp o C. General procedure for the large scale synthesis of 5c Table S6. Large scale synthesis of 5c. Substrate Product Yield 3bA 5cA 54 3bC 5cC 22 3bD 5cD 27 3bE 5cE 47 3bF 5cF 25 3bG 5cG 42 Suspension of Pt(cod)Cl 2 (2.24 g, 6.00 mmol), 3bA (5.38 g, 6.00 mmol), and K 3PO 4 (5.10 g, 24.0 mmol) in THF (1200 ml) was heated at 65 o C for 18 h under a nitrogen atmosphere. To the resulting mixture was added water, and was extracted with CH 2Cl 2. The combined organic layers were washed with brine, dried over Na 2SO 4, filtered through a pad of Celite, and concentrated under reduced pressure to give a crude mixture. The residue was washed with hexane to give a gray solid. A suspension of above obtained solid (5.50 g) and PPh 3 (3.93 g, 15.0 mmol) in toluene (150 ml) was heated at 105 C for 18 h under nitrogen atmosphere. The resulting suspension was filtered through a pad of silica gel using CH 2Cl 2 as the eluent, and the filtrate was concentrated under reduced pressure to give a crude mixture. The residue was purified by silica gel chromatography (hexane/ch 2Cl 2 = 5:1 to 1:1) to give 6b (2.94 g, 54%) as a white solid. S14

15 5cC: The title compound was prepared from 3bC (7.00 g, 6.72 mmol), Pt(cod)Cl 2 (2.52 g, 6.72 mmol), K 3PO 4 (7.14 g, 33.6 mmol), and PPh 3 (4.4 g, 16.8 mmol) according to the general procedure. Yellow solid (1.24 g, 22% in two yield) 5cD: The title compound was prepared from 3bD (10.0 g, 9.11 mmol), Pt(cod)Cl 2 (3.41 g, 9.11 mmol), K 3PO 4 (9.67 g, mmol) and PPh 3 (5.98 g, 22.8 mmol) according to the general procedure. Yellow solid (2.05 g, 27% in two yield) 5cE: The title compound was prepared from 3bE (4.82 g, 4.18 mmol), Pt(cod)Cl 2 (1.56 g, 4.18 mmol), K 3PO 4 (4.44 g, 20.9 mmol), and PPh 3 (2.74 g, 10.5 mmol) according to the general procedure. Yellow solid (1.77 g, 47% in two yield) 5cF: The title compound was prepared from 3bF (8.50 g, 7.37 mmol), Pt(cod)Cl 2 (2.76 g, 7.37 mmol), K 3PO 4 (7.82 g, mmol), and PPh 3 (4.83 g, 18.1 mmol) according to the general procedure. Yellow solid (1.65 g, 25% in two yield) 5cG: The title compound was prepared from 3bF (5.55 g, 5.00 mmol), Pt(cod)Cl 2 (1.87 g, 5.00 mmol), K 3PO 4 (5.31 g, 25.0 mmol), and PPh 3 (3.28 g, 12.5 mmol) according to the general procedure. Yellow solid (1.80 g, 42% in two yield). Synthesis of 5d Table S7. Synthesis of 5d. Substrate Product Yield (%) 5cA 5dA 97 5cC 5dC 99 5cD 5dD 99 5cE 5dE 99 5cF 5dF 96 5cG 5dG 99 General procedure for the synthesis of 5d. 5dA. To a solution of 5cC (2.60 g, 2.02 mmol) in THF (200 ml) was added TBAF (8.90 ml, 1.00 M in THF, 8.90 mmol) at room temperature. After stirring for 2 h at this temperature, the reaction mixture was quenched with water. THF was evaporated, and the resulting solid was collected by filtration, and washed with water and ether to give 5dA as a colorless solid (1.62 g, 97 %). Due to the low solubility of 5dA in common deuterated solvents, a sufficient signal-to-noise ratio could not be obtained to perform 1 H and 13 C NMR measurements. IR S15

16 (KBr) 732, 810, 1005, 1230, 1425, 1628, 2855, 2896, 3438 (brs), 3520 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 60H 45O 4 [M + H] -, , found ; d.p. > 250 o C. 5dC: The title compound was prepared from 5cC (1.24 g, mmol) and TBAF (3.94 ml, 1.00 M in THF, 3.94 mmol) according to the general procedure. Yellow solid (870 mg, 99% yield). 1 H NMR (CDCl 3, 400 MHz) = 0.97 (t, 6H, J = 7.6 Hz, -CH 3), 0.97 (t, 6H, J = 7.6 Hz, -CH 3), 1.45 (sext, 4H,, J = 7.6 Hz, -CH 2-), 1.48 (sext, 4H,, J = 7.6 Hz, -CH 2-), 1.76 (quin, 4H, J = 7.6 Hz, -CH 2-), 1.79 (quin, 4H, J = 7.6 Hz, -CH 2-), 3.28 (s, 2H, -OH), 3.34 (s, 2H, -OH), 3.97 (t, 4H, J = 6.4 Hz, -OCH 2-), 3.98 (t, 4H, J = 6.4 Hz, -OCH 2-), 5.47 (s, 2H, -CH=C(OBu)-), 5.51 (s, 2H, -CH=C(OBu)-), 6.93 (d, 4H, J = 8.4 Hz, -Ar), 6.99 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.4 Hz, -Ar), 7.13 (d, 4H, J = 8.4 Hz, - Ar), 7.30 (d, 4H, J = 8.4 Hz, -Ar), 7.32 (d, 4H, J = 8.4 Hz, -Ar), 7.46 (d, 4H, J = 8.4 Hz, -Ar), 7.47 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 13.82, 13.83, 19.35, 19.39, 30.90, 30.94, 67.84, 67.92, 73.57, 73.65, , , , , , , , , , , , , , , , , , , , ppm; IR (KBr) 814, 1003, 1057, 1211, 1366, 1487, 1645, 2872, 2928, 3445 (br), 3580 cm -1 ; HRMS (ESI- TOF) m/z: Calcd for C 76H 77O 8 [M + H] -, , found ; d.p. > 210 o C. 5dD: The title compound was prepared from 5cD (1.90 g, 1.13 mmol) and TBAF (5.63 ml, 1.00 M in THF, 5.63 mmol) according to the general procedure. Yellow solid (1.38 g, 99% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 12H, -CH 3), (m, 40H, -CH 2-), 1.79 (quin, 8H, J = 7.2 Hz, -CH 2-), 3.29 (s, 2H, -OH), 3.35 (s, 2H, -OH), 3.96 (t, 4H, J = 6.4 Hz, -OCH 2-), 3.98 (t, 8H, J = 6.4 Hz, -OCH 2-), 5.47 (s, 2H, -CH=C(OHex)-), 5.51 (s, 2H, -CH=C(OHex)-), 6.93 (d, 4H, J = 8.4 Hz, -Ar), 6.99 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.4 Hz, -Ar), 7.30 (d, 4H, J = 8.4 Hz, -Ar), 7.32 (d, 4H, J = 8.0 Hz, -Ar), 7.47 (d, 4H, J = 8.0 Hz, -Ar), 7.48 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) = 14.00, 14.00, 22.53, 22.55, 25.77, 25.81, 28.80, 28.83, 31.51, 31.51, 68.14, 68.22, 73.54, 73.63, , , , , , , , , , , , , , , , , , , , ppm; IR (KBr) 814, 1003, 1063, 1211, 1366, 1487, 1645, 2871, 2932, 3431 (br), 3580 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 82 H 89 O 8 [M + H] -, , found ; d.p. > 210 o C. 5dE: The title compound was prepared from 5cE (1.77 g, mmol) and TBAF (4.92 ml, 1.00 M in THF, 4.92 mmol) according to the general procedure. Yellow solid (1.31 g, 99% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 12H, -CH 3), (m, 40H, -CH 2-), 1.79 (quin, 8H, J = 7.2 Hz, -CH 2-), 3.28 (s, 2H, -OH), 3.34 (s, 2H, -OH), 3.96 (t, 4H, J = 6.4 Hz, -OCH 2-), 3.97 (t, 8H, J = 6.4 Hz, -OCH 2-), 5.46 (s, 2H, -CH=C(OOct)-), 5.51 (s, 2H, -CH=C(OOct)-), 6.93 (d, 4H, J = 8.4 Hz, -Ar), 6.99 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.4 Hz, -Ar), 7.30 (d, 4H, J = 8.4 Hz, -Ar), 7.32 (d, 4H, J = 8.0 Hz, -Ar), 7.46 (d, 4H, J = 8.0 Hz, -Ar), 7.47 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 14.07, 14.07, 22.62, 22.62, 26.10, 26.14, 28.83, S16

17 28.86, 29.17, 29.19, 29.29, 29.29, 31.78, 31.78, 68.14, 68.20, 73.53, 73.62, , , , , , , , , , , , , , , , , , , , ppm; IR (KBr) 814, 1003, 1057, 1209, 1364, 1487, 1645, 2857, 2928, 3447 (br), 3580 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 92 H 108 O 8 [M + H] -, , found ; d.p. > 200 o C. 5dF: The title compound was prepared from 5cF (1.65 g, mmol) and TBAF (4.59 ml, 1.00 M in THF, 4.59 mmol) according to the general procedure. Yellow solid (1.19 g, 96% yield). 1 H NMR (CDCl 3, 400 MHz) = (m, 24H, -CH 3), (m, 32H, -CH 2-), 1.74 (sept, 4H, J = 6.4 Hz, -CH-), 3.25 (s, 1H, -OH), 3.25 (s, 1H, -OH), 3.31 (s, 1H, -OH), 3.32 (s, 1H, -OH), (m, 8H, -OCH 2-), 5.47 (s, 1H, -CH=C(OEtHex)-), 5.47 (s, 1H, -CH=C(OEtHex)-), 5.52 (s, 1H, - CH=C(OEtHex)-), 5.53 (s, 1H, -CH=C(OEtHex)-), 6.93 (d, 4H, J = 8.4 Hz, -Ar), 6.98 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.4 Hz, -Ar), 7.12 (d, 4H, J = 8.0 Hz, -Ar), 7.30 (d, 4H, J = 8.0 Hz, -Ar), 7.32 (d, 4H, J = 8.0 Hz, -Ar), 7.46 (d, 4H, J = 8.4 Hz, -Ar), 7.47 ppm (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 11.08, 11.15, 14.05, 14.06, 23.00, 23.90, 23.95, 24.03, 24.06, 28.96, 29.08, 29.10, 30.48, 30.52, 30.65, 30.68, 39.08, 39.13, 70.44, 70.50, 73.67, 73.75, , , , , , , , , , , , , , , , , , , ppm; IR (KBr) 814, 1003, 1063, 1209, 1368, 1487, 1645, 2827, 2928, 3447 (br), 3587 cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 92 H 108 O 8 [M + H] -, , found ; d.p. > 250 o C. 5dG: The title compound was prepared from 5cG (2.53 g, 1.48 mmol) and TBAF (7.40 ml, 1.00 M in THF, 7.40 mmol) according to the general procedure. Yellow solid (1.83 g, 99% yield). 1 H NMR (DMSO-d 6, 400 MHz): = 4.98 (ABq, 8H, Δδ AB = 0.05, J AB = 12.8 Hz, -OCH 2-), 5.50 (brs, 4H, -OH), 5.66 (s, 4H, -CH=C(OBn)-), 6.98 (d, 8H, J = 8.4 Hz, -Ar), 7.11 (d, 8H, J = 8.4 Hz, -Ar), (m, 20H, -Ar), 7.50 (d, 8H, J = 6.8 Hz, -Ar), 7.55 ppm (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 68.85, 72.67, , , , , , , , , , , , , ppm; IR (KBr) 795, 1030, 1225, 1365, 1467, 1655, 2825, 2923, 3429 (br) cm -1 ; HRMS (ESI-TOF) m/z: Calcd for C 88 H 68 O 8 [M + H] -, , found ; d.p. > 300 o C. S17

18 Synthesis of 6 Table S8. Synthesis of 6. Substrate Temperature Product Yield 5dA reflux 6A 92% (1.30 g) 5dC rt 6C 96% (540 mg) 5dD rt 6D 93% (1.06 g) 5dE rt 6E 92% (1.15 g) 5dF rt 6F 78 (857 mg) 5dG rt 6G 89 (1.26 g) General procedure for the synthesis of 6. 6A. To a solution of SnCl2 2H2O (1.84 g, 8.14 mmol) in THF (10 ml) was added conc. HCl (1.36 ml, 12 N, 16.3 mmol) at room temperature. After stirring for 0.5 h at this temperature, the resulting solution was added to a suspension of 5dA (1.53 g, 1.85 mmol) in THF (500 ml), and the resulting mixture was refluxed for 12 h. The solvent was removed under reduced pressure, and the residue was purified by passing over a short silica gel plug with CH 2Cl 2 as an eluent. The resulting solid was dispersed in MeOH, filtered, and washed with MeOH to give 6A (1.30 g, 92%) as a pale-yellow solid. The NMR spectra were consistent with literature data. 5 6C: The title compound was prepared from 5dC (600 mg, mmol), SnCl2 2H2O (533 mg, 2.36 mmol), and HCl (0.394 ml, 4.73 mmol) according to the general procedure. Yellow solid (540 mg, 96% yield). 1 H NMR (CDCl 3, 400 MHz) 0.90 (t, 12H, J = 7.6 Hz, -OBu), 1.40 (t, 8H, J = 7.6 Hz, - OBu), 1.69 (quin, 8H, J = 7.6 Hz, -OBu), 3.84 (t, 8H, J = 6.4 Hz, -OBu), 6.85 (s, 4H, -Ar), 7.48 (d, 8H, J = 8.4 Hz, -Ar), 7.54 (d, 8H, J = 8.4 Hz, -Ar), 7.60 (d, 8H, J = 8.4 Hz, -Ar), 7.62 (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) 13.87, 19.42, 31.65, 69.60, , , , , , , , , , , ; IR (KBr) 746, 814, 1003, 1204, 1377, 1483, 1600, 2870, 2957 cm -1 HRMS (MALDI-TOF) m/z: calcd for C 76H 72O 4 (M) + : , found d.p. > 250 o C. 6D: The title compound was prepared from 5dD (1.21 g, mmol), SnCl2 2H2O (977 mg, 4.33 mmol), and HCl (0.720 ml, 8.66 mmol) according to the general procedure. Yellow solid (1.06 g, 93% yield). 1 H NMR (CDCl 3, 400 MHz): = 0.86 (t, 12H, J = 6.8 Hz, -OHex), (m, 24H, - OHex), (m, 8H, -OHex), 3.84 (t, 8H, J = 6.4 Hz, -OHex), 6.86 (s, 4H, -C 6H 2(OHex) 2), 7.48 (d, 8H, J = 8.8 Hz, -Ar), 7.53 (d, 8H, J = 8.8 Hz, -Ar), 7.60 (d, 8H, J = 8.8 Hz, -Ar), 7.63 ppm (d, 16H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 14.03, 22.59, 25.82, 29.47, 31.56, 69.86, , S18

19 126.56, , , , , , , , , ppm; IR (KBr) 746, 812, 1003, 1206, 1377, 1483, 1595, 2866, 2953 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 84H 88O 4 (M) +, , found ; d.p. > 250 o C. 6E: The title compound was prepared from 5dE (1.31 g, mmol), SnCl2 2H2O (969 mg, 4.30 mmol), and HCl (0.716 ml, 8.59 mmol) according to the general procedure. Yellow solid (1.15 mg, 92% yield). 1 H NMR (CDCl 3, 400 MHz): = 0.83 (t, 12H, J = 6.8 Hz, -OOct), (m, 40H, - OOct), 1.70 (qnt, 8H, J = 6.8 Hz, -OOct), 3.83 (t, 8H, J = 6.4 Hz, -OOct), 6.85 (s, 4H, -C 6H 2(OOct) 2), 7.47 (d, 8H, J = 8.8 Hz, -Ar), 7.53 (d, 8H, J = 8.8 Hz, -Ar), 7.59 (d, 8H, J = 8.8 Hz, -Ar), 7.63 ppm (d, 16H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 14.11, 22.67, 26.16, 29.26, 29.35, 29.52, 31.81, 69.85, , , , , , , , , , , ppm; IR (KBr) 746, 812, 1001, 1206, 1377, 1483, 1593, 2855, 2926 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 92H 104O 4 [M] +, , found ; d.p. > 250 o C. 6F: The title compound was prepared from 5cF (1.16 g, mmol), SnCl2 2H2O (0.858 g, 3.80 mmol), and HCl (0.633 ml, 7.61 mmol) according to the general procedure. Yellow solid (857 mg, 78% yield). 1 H NMR (CDCl 3, 400 MHz): = 0.83 (t, 12H, J = 6.8 Hz, -OEtHex), 0.83 (t, 12H, J = 7.6 Hz, -EtHex), (m, 32H, -OEtHex), 1.63 (sept, 4H, J = 6.4 Hz, -OEtHex), 3.75 (d, 4H, J = 2.0 Hz, -OEtHex), 3.76 (d, 4H, J = 2.0 Hz, -OEtHex), 6.84(s, 4H, -C 6H 2(OEtHex) 2), 7.47 (d, 8H, J = 8.8 Hz, -Ar), 7.53 (d, 8H, J = 8.8 Hz, -Ar), 7.59 (d, 8H, J = 8.8 Hz, -Ar), 7.61 ppm (d, 8H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz): = 11.21, 14.07, 23.03, 23.96, 29.09, 30.60, 39.78, 71.71, , , , , , , , , , , ppm; IR (KBr) 746, 812, 1003, 1204, 1377, 1483, 1593, 2870, 2957 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 92H 104O 4 [M] +, , , found ; d.p. > 250 o C. 6G: The title compound was prepared from 5cH (1.51 g, 1.20 mmol), SnCl2 2H2O (1.19 g, 5.28 mmol), and HCl (0.880 ml, 10.6 mmol) according to the general procedure. Yellow solid (1.26 g, 89% yield). 1 H NMR (CDCl 3, 400 MHz): = 4.90 (s, 8H, -OCH 2Ph), 6.95 (s, 4H, -C 6H 2(OBn) 2), (m, 20H, -OCH 2Ph), 7.46 (d, 8H, J = 8.4 Hz, -Ar), 7.53 (d, 8H, J = 8.4 Hz, -Ar), 7.60 (d, 8H, J = 8.8 Hz, -Ar), 7.61 ppm (d, 8H, J = 8.8 Hz, -Ar); Due to the low solubility of 6G in common deuterated solvents, a sufficient signal-to-noise ratio could not be obtained to perform 13 C NMR measurement; IR (KBr) 746, 814, 1003, 1204, 1377, 1483, 1599, 2870, 2957 cm -1 ; HRMS (MALDI-TOF) m/z: Calcd for C 88H 64O 4 [M] +, , found ; d.p. > 300 o C. S19

20 Figure S1. Cyclic voltammograms of 6A and 6C-G (1.0 mmol L -1 ) in 0.1 mol L -1 Bu 4NPF 6/1,1,2,2- tetrachloroethane at room temperature at a scan rate = 0.1 V s -1. Figure S2. (a) UV vis absorption and fluorescence spectra of 6A and 6C-G in CHCl 3. (b) Fluorescent emission of the representative samples in CHCl 3. Electron-only device Device with the following structure was fabricated: ITO (150nm)/ 6C (80 nm)/bcp (10 nm)/liq (1 nm)/ Al (80 nm), where ITO, BCP, and Liq are indium tin oxide, 2,9-Dimethyl-4,7-diphenyl-1,10- S20

21 phenanthroline, and 8-quinolinolato, respectively. The ITO substrate was pre-cleaned with acetone and 2-propanol followed by ultraviolet light and ozone irradiation for 30 min. The 6C layer was formed with the spin-coating method: The chlorobenzene solution of 6C (14 mg / ml, stirred at 80 C for 40 min) was spin-coated on the pre-cleaned ITO substrate at 600 rpm for 30 s and then dried under vacuum at 120 C for 30 min. Then, BCP, Liq, and Al were sequentially deposited. BCP and Liq were deposited at a pressure of Pa and deposition rate of <0.05 nm s 1. Al was deposited at a pressure of Pa and deposition rate of <0.15 nm s 1. Current density-voltage (J-V) characteristic was measured with a PC-controlled source meter (2400, Keithley, Japan). The thickness of the organic layer was measured by a stylus surface profiler (Dektak 6M, Veeco Instruments Inc., USA). The J-V characteristic showed SCLC in the region of MV cm -1. The SCLC in this region was fitted according to the Mott-Gurney theory and expressed in equation (1), J SCLC = 9 ε 8 0εμ V2 L3, (1) and the electron mobility was fitted assuming the Pool-Frenkel model expressed in equation (2), μ = μ 0 exp (0.89β E), (2) where J is the current density, ε 0 is the permittivity of the free space, ε is the dielectric constant of 3, μ is the carrier mobility, V is the applied voltage, L is the thickness of the organic layer, μ 0 is the zero field carrier mobility, β is the Pool-Frenkel coefficient, and E is the electric field defined as the applied voltage per the thickness of the organic layer. Figure S3. The J V curve of the electron only device of 6C. S21