Supporting Information

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1 Supporting Information Synthesis and Characterization of [5]Cycloparaphenylene Eiichi Kayahara,, Vijay Kumar Patel,, and Shigeru Yamago*,, Institute for Chemical Research, Kyoto University, Uji, Kyoto , Japan. CREST, Japan Science and Technology Agency (JST), Japan. *To whom correspondence should be addressed. General. All reactions dealing with air- and moisture sensitive compounds were carried out in a dry reaction vessel under nitrogen atmosphere. Water content in solvents was determined by Karl-Fisher water titrator. 1 H (400 MHz) and 13 C NMR (100 MHz) spectra were measured for a CDCl 3 or acetone-d 6 solution of a sample and are reported in parts per million ( ) from internal tetramethylsilane or residual solvent peak. Electrospray ionization time-of-flight mass (ESI-TOF MS) spectrum was recorded on a spectrometer in the positive mode. A sample was injected as a CH 2 Cl 2 /isopropanol solution. 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 tetrahydrofuran (THF) solution by mixing a sample (1 mg/ml) and dithranol (10 mg/ml) in a 1:1 ratio. UV and emission spectra were measured in CHCl 3 at room temperature. Cyclic voltammetry (CV) was measured with a Pt electrode for 1,1,2,2-tetrachloroethane or THF solution of a sample (1 mmol L -1 ) in the presence of an supporting electrolyte (Bu 4 NPF 6, 0.10 mol L -1 ) at room temperature under nitrogen atmosphere. The scan rates of 0.1 or 0.05 V s 1 were employed. After the measurement, ferrocene was added to the sample solution, and the potentials were calibrated against the ferrocene/ferrocenium couple (Fc/Fc + ). Materials. Unless otherwise noted, commercially available materials were used without purification. Dichloromethane (CH 2 Cl 2 ) and 1,1,2,2-tetrachloroethane was distilled successively from P 2 O 5 and K 2 CO 3 and stored over molecular sieves. Toluene and DMF were distilled from CaH 2 and stored over molecular sieves. Dibromide 1a, (4-bromophenyl)-4-hydroxy-2,5-cyclohexadien-1-one (4), 1,3 4-bromo-4'-[[(1,1-dimethylethyl)- dimethylsilyl]oxy]-1,1'-biphenyl, 1 dichloro(1,5-cyclooctadiene)platinum [Pt(cod)Cl 2 ], 4 and bis(1,5-cyclooctadiene)nickel [Ni(cod) 2 ] 5 were synthesized as reported. Synthesis of 1,4-bis[4-(4-trimethylstannyl phenyl)-1,4-dimethoxy-2,5-cyclohexadien-1-yl]- benzene (1a ). To a solution of 1a (0.665 g, 1.00 mmol) in THF (10 ml) was added BuLi (1.41 ml, 1.56 M in hexane, 2.20 mmol) S1 --

2 through a syringe at 78 ºC over 5 min. After stirring for 0.5 h at this temperature, a solution of trimethylstannyl chloride (0.500 g, 2.50 mmol) in THF (1 ml) was slowly added through a cannula at -78 o C, and the resulting mixture was slowly warmed to room temperature. After stirring for 3 h at this temperature, the reaction mixture was quenched with saturated aqueous NH 4 Cl solution, and was extracted with ethyl acetate. The combined organic layer was washed with saturated aqueous NaCl solution, dried over MgSO 4, filtered and concentrated under reduced pressure to give a crude mixture. The crude mixture was purified by passing it over neutral alumina with hexane as the eluent, to give 1a (0.772 g, 93%) as a white solid. 1 H NMR (CDCl 3, 400 MHz) 0.27 (s, 18H, J Sn-H = 54.0 Hz, SnMe 3 ), 3.42 (s, 12H, -OCH 3 ), 6.08 (s, 8H, -CH=CH-), (m, 12H, -Ar); 13 C NMR (CDCl 3, 100 MHz) -9.56, 51.94, 74.60, 74.66, , , , , , , , ; HRMS (FAB-MS) m/z: Calcd for C 40 H 50 O 4 Sn 2 (M) +, , found u; IR (KBr) 760, 826, 855, 943, 1078, 1171, 1186, 1400, 2821, 2936, 2974; mp o C. Synthesis of 3a. Pt(cod)Cl 2 (0.190 g, mmol) and 1a (0.416 g, mmol) were dissolved in THF (40 ml), and the mixture was heated at 60 o C for 20 h under a nitrogen atmosphere. To the resulting mixture was added water, and was extracted with CH 2 Cl 2. The combined organic layer was washed with brine, dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. A solution of the crude platinum complex and PPh 3 (0.289 g, 1.10 mmol) in toluene (10 ml) was heated at 95 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 2 Cl 2 = 2:1), and subsequent preparative gel permeation chromatography using chloroform as the eluent giving 3a (0.131 g, 52%) as a white solid. 1 H NMR (CDCl 3, 400 MHz) 3.56 (s, 6H, -OCH 3 ), 3.46 (s, 6H, -OCH 3 ), 5.74 (dd, 4H, J = 8.8, 1.6 Hz, -CH=CH-), 5.99 (s, 4H, -Ar), 6.59 (dd, 4H, J = 8.8, 1.6 Hz, -CH=CH-), 7.46 (s, 4H, -Ar), 7.46 (s, 4H, -Ar); 13 C NMR (CDCl 3, 100 MHz) 51.27, 52.68, 73.62, 74.90, , , , , , , , ; HRMS (MALDI-TOF) m/z: Calcd for C 34 H 32 O 4 Ag (M + Ag) +, , found ; IR (neat) 530, 665, 758, 818, 835, 951, 1082, 1175, 1229, 1404, 1449, 1503, 2361, 2824, 2937; mp o C. Synthesis of 3a by Ni(0)-mediated Yamamoto-coupling reaction. Ni(cod) 2 (0.551 g, 2.00 mmol) and 2,2 -bipyridyl (0.312 g, 2.00 mmol) were dissolved in THF (100 ml), and the mixture was stirred at 50 o C for 0.5 h under a nitrogen atmosphere. The resulting mixture was added to a solution of 1a (0.664 g, 1.00 mmol) in THF (400 ml), and the resulting mixture was refluxed for 15 h. The reaction mixture was passed through a pad of Celite with ethyl acetate as the eluent 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 2e (0.256 g, 51 %) as a white solid. Synthesis of 4'-[4-(4-bromophenyl)-1,4-bis(triethylsiloxy)-2,5-cyclohexadien-1-yl]- [1,1'-biphenyl]-4-ol (5e). A solution of 4 (10.0 g, 37.7 mmol) in 150 ml of THF was slowly added to a slurry of sodium hydride (1.96 g, 49.0 mmol, 60% in mineral oil) in 100 ml of THF at -78 o C through a cannula, and then the resulting mixture was stirred for 0.5 h at same temperature. In a separate flask, to a solution of S2 --

3 4-bromo-4'-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-1,1'-biphenyl (28.8 g, 79.2 mmol) in THF (220 ml) was slowly added BuLi (56.0 ml, 1.49 M in hexane, 83.2 mmol) at -78 C using a syringe. After stirring for 1 h at same temperature, to the resulting solution was added the solution of 4 above prepared through a cannula. After stirring for 2 h at same temperature, the reaction mixture was quenched with saturated aqueous NH 4 Cl solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. After confirming the presence of diol by 1 H-NMR, the crude mixture was used to the next step without further purification. To a solution of the crude diol and imidazole (10.3 g, 151 mmol) in DMF (100 ml) was slowly added chlorotriethylsilane (19.0 ml, 113 mmol) at room temperature. After stirring for 9 h at 40 o C, the reaction mixture was quenched with saturated aqueous NaHCO 3 solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. After confirming the presence of 5d by 1 H-NMR, the crude mixture was used to the next step without further purification. To a solution of the crude mixture in DMF (70 ml) was added LiOH (8.30 g, 198 mmol), and the resulting mixture was stirred at room temperature for 11 h. The reaction mixture was diluted with ethyl acetate, washed with water and saturated aqueous NaCl solution, dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. Purification by silica gel chromatography (hexane/ethyl acetate = 8:1) afforded 5e in 92 % yield (23.0 g) over 3 steps from 4 as a pale yellow oil. 5d: 1 H NMR (CDCl 3, 400 MHz) 0.23 (s, 6H, -SiMe 2 t-bu), 0.60 (q, 6H, J = 7.6 Hz, -SiEt 3 ), 0.60 (q, 6H, J = 7.6 Hz, -SiEt 3 ), 0.93 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 0.94 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 1.00 (s, 9H, -SiMe 2 t-bu), 5.94 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.04 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.89 (d, 2H, J = 8.8 Hz, -Ar), 7.21 (d, 2H, J = 8.4 Hz, -Ar), 7.36 (d, 2H, J = 8.4 Hz, -Ar), 7.37 (d, 2H, J = 8.8 Hz, -Ar), 7.46 (m, 4H, -Ar); 13 C NMR (CDCl 3, 100 MHz) -4.38, 6.41, 6.45, 7.03, 18.24, 25.70, 71.23, , , , , , , , , , , , , , , , ; HRMS (FAB-MS) m/z: Calcd for C 42 H 61 BrO 3 Si 3 (M) +, , found ; IR (neat) 737, 823, 839, 914, 1074, 1263, 1472, 1493, 2876, e: 1 H NMR (CDCl 3, 400 MHz) 0.60 (q, 6H, J = 7.2 Hz, -SiEt 3 ), 0.62 (q, 6H, J = 7.2 Hz, -SiEt 3 ), 0.94 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 0.96 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 4.87 (s, 1H, -OH), 5.94 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.04 (d, 2H, J = 10.4 Hz, -CH=CH-), 6.89 (d, 2H, J = 8.8 Hz, -Ar), 7.22 (d, 2H, J = 8.4 Hz, -Ar), 7.35 (d, 2H, J = 8.8 Hz, -Ar), 7.38 (d, 2H, J = 8.8 Hz, -Ar), 7.46 (m, 4H, -Ar); 13 C NMR (CDCl 3, 100 MHz) 5.76, 6.41, 6.44, 6.55, 7.03, 25.62, 71.22, 71.23, , , , , , , , , , , , , , ; HRMS (FAB-MS) m/z: Calcd for C 36 H 47 BrO 3 Si 2 (M) +, , found ; IR (neat) 729, 818, 909, 1005, 1435, 1238, 1263, 1479, 1495, 1605, 2876, 2955, 3251 (br). Synthesis of 1,4-bis[4-(4-bromophenyl)-1,4-bis(triethylsiloxy)-2,5-cyclohexadien-1-yl]- benzene (1c). Diacetoxyiodobenzene (7.30 g, 22.6 mmol) was added slowly to a solution of 5e (10.0 g, 15.1 mmol) in a mixture of THF (80 ml), CH 3 CN (20 ml) and H 2 O (25 ml) at room temperature over the course of 30 min. After stirring for 2.5 h at same temperature, the reaction mixture was quenched with saturated aqueous NaHCO 3 solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, S3 --

4 dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. After confirming the presence of 6 by 1 H-NMR, the crude mixture was used to the next step without further purification. A solution of the crude mixture in 50 ml of THF was slowly added to a slurry of sodium hydride (0.788 g, 19.6 mmol, 60% in mineral oil) in 75 ml of THF at -78 o C through a cannula, and then the resulting mixture was stirred for 0.5 h at same temperature. In a separate flask, to a solution of 1,4-dibromobenzene (7.50 g, 31.7 mmol) in THF (100 ml) was slowly added BuLi (21.0 ml, 1.55 M in hexane, 33.2 mmol) at -78 C using a syringe. After stirring for 1 h at same temperature, to the resulting solution was added above prepared solution of 6 through a cannula. After stirring for 2.5 h at same temperature, the reaction mixture was quenched with saturated aqueous NH 4 Cl solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. After confirming the presence of diol by 1 H-NMR, the crude mixture was used to the next step without further purification. To a solution of the crude diol and imidazole (4.10 g, 60.4 mmol) in DMF (50 ml) was slowly added chlorotriethylsilane (7.60 ml, 45.3 mmol) at room temperature. After stirring for 10 h at 40 o C, the reaction mixture was quenched with saturated aqueous NaHCO 3 solution, and was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution, dried over Na 2 SO 4, filtered and concentrated under reduced pressure to give a crude mixture. Purification by silica gel chromatography (hexane/ethyl acetate = 20:1) afforded 1c in 53% yield (8.53 g) over 3 steps from 5e as a pale yellow oil. 1c: 1 H NMR (CDCl 3, 400 MHz) 0.56 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.62 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.91 (t, 18H, J = 7.6 Hz, -SiEt 3 ), 0.94 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 5.90 (d, 4H, J = 10.0 Hz, -CH=CH-), 6.02 (d, 4H, J = 10.4 Hz, -CH=CH-), 7.16 (dd, 4H, J = 6.8, 2.0 Hz, -Ar), 7.24 (s, 2H, -Ar), 7.35 (dd, 4H, J = 6.8, 2.0 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) 6.39, 6.45, 7.01, 7.03, 71.11, 71.23, , , , , , , , ; HRMS (FAB-MS) m/z: Calcd for C 54 H 80 Br 2 O 4 Si 4 (M) +, , found ; IR (neat) 540, 716, 733, 961, 1011, 1072, 1188, 1240, 1406, 1456, 1479, 2876, 2910, Synthesis of 3c. Ni(cod) 2 (0.52 g, 1.88 mmol) and 2,2 -bipyridyl (0.29 g, 1.88 mmol) were dissolved in THF (70 ml), and the mixture was stirred at 50 o C for 0.5 h under a nitrogen atmosphere. The resulting mixture was added to a solution of 1c (1.00 g, 0.94 mmol) in THF (400 ml), and the resulting mixture was refluxed for 15 h. The reaction mixture was passed through a pad of Celite with ethyl acetate as the eluent 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 2e (0.53 g, 63 %) as a white solid. 1 H NMR (CDCl 3, 400 MHz) 0.61 (q, 12H, J = 8.4 Hz, -SiEt 3 ), 0.65 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 5.59 (d, 4H, J = 10.0 Hz, -CH=CH-), 5.87 (s, 4H, -Ar), 6.35 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.43 (s, 8H, -Ar); 13 C NMR (CDCl 3, 100 MHz) 6.45, 6.46, 6.93, 7.02, 69.67, 71.91, , , , , , , , ; HRMS (MALDI-TOF) m/z: Calcd for C 54 H 80 O 4 Si 4 Ag (M + Ag) +, , found ; IR (neat) 741, 962, 1012, 1088, 1168, 1238, 1415, 2875, Synthesis of 3b. To a solution of 3c (0.50 g, 0.55 mmol) in THF (5 ml) was added TBAF (2.30 ml, 1.00 M in S4 --

5 THF, 2.30 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 CHCl 3 to give 3b as white solid (0.23 g, 94 %). 1 H NMR (CDCl 3, 400 MHz) 4.40 (s, 2H, -OH), 4.92 (s 2H, -OH), 5.60 (d, 4H, J = 10.0 Hz, -CH=CH-), 5.97 (s, 4H, -Ar), 6.45 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.52 (t, 4H, J = 8.8 Hz, -Ar), 7.55 (t, 4H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3, 100 MHz) 68.48, 70.28, , , , , , , , ; HRMS (ESI-TOF) m/z: Calcd for C 30 H 24 O 4 Na (M + Na) +, , found ; IR (KBr) 584, 770, 827, 951, 1032, 1192, 1398, 3325 (br); dp 273 o C. Synthesis of [5]CPP. A solution of 3b (22.5 mg, 0.05 mmol) and SnCl 2 H 2 O (40.6 mg, 0.50 mmol) in THF (10 ml) was heated at 60 C for 6 h under nitrogen atmosphere. To the resulting mixture was added 10% aqueous NaOH solution, and was extracted with CH 2 Cl 2. The combined organic layer was washed with brine, dried over MgSO 4, filtered and concentrated under reduced pressure to give a crude mixture. The residue was purified by silica gel chromatography (hexane/ch 2 Cl 2 = 1:1 to 1:2), giving [5]CPP (11.0 mg, 58%) as an dark purple solid. 1 H NMR (CDCl 3, 400 MHz) 7.85 (s, 20H, -Ar); 13 C NMR (CDCl 3, 100 MHz) , ; HRMS (MALDI-TOF) m/z: calcd for C 30 H 20 [M] + : , found Electrochemical analysis. Electrochemical analysis of [5]CPP was performed in 0.1 mol L -1 Bu 4 NPF 6 solution of 1,1,2,2-tetrachloroethane or THF by using cyclic voltammetry (Figures S1 and S2). Current (10-5 A) E ox 1/2 = V, V (in THF) E red 1/2 = V, V (in THF) Potential (V) vs. Fc/Fc + Figure S1. Cyclic voltammogram of [5]CPP in Bu 4 NPF 6 /THF at room temperature; scan rate = 0.1 (for oxidation) and 0.05 (for reduction) V/s. S5 --

6 Current (10-5 A) Potential (V) vs. Fc/Fc + Figure S2. Cyclic voltammogram of [5]CPP in Bu 4 NPF 6 /THF at room temperature; scan rate = 0.05 V/s. Red curve (scan range = -1.0 ~ V); blue curve (scan range = ~ V). Computational Study. DFT calculations were carried using the Gaussian 09 program package. 10 The density functional theoretical (DFT) method was employed using the B3LYP hybrid functional with the 6-31G(d) basis set. 13 Table S1. TD-DFT vertical one-electron excitations calculated for [5]CPP. Energy (ev) Wavelength (nm) Oscillator strength (f) Contributions HOMO LUMO ( ) HOMO LUMO+4 ( ) HOMO-2 LUMO ( ) HOMO-1 LUMO ( ) HOMO LUMO+1 ( ) HOMO-2 LUMO ( ) HOMO LUMO+2 ( ) HOMO LUMO+6 ( ) HOMO-6 LUMO+6 ( ) HOMO-5 LUMO ( ) HOMO-3 LUMO ( ) HOMO-5 LUMO ( ) HOMO-3 LUMO ( ) HOMO LUMO+8 ( ) HOMO LUMO+9 ( ) S6 --

7 Figure S3. Energy diagram and HOMO-2, HOMO-1, HOMO, LUMO, LUMO+1, and LUMO+2 orbitals of [5]CPP. Surfaces are drawn at an isodensity value of The values indicate the energy level (ev). Excitation energies were computed by TD-DFT at the same level. References (1) Xia, J.; Jasti, R. Angew. Chem. Int. Ed. 2012, 51, (2) Xia, J.; Bacon, J. W.; Jasti, R. Chem. Sci. 2012, 3, (3) Sisto, T. J.; Golder, M. R.; Hirst, E. S.; Jasti, R. J. Am. Chem. Soc. 2011, 133, (4) Hill, G. S.; Irwin, M. J.; Levy, C. J.; Rendina, L. M.; Puddephatt, R. J.; Andersen, R. A.; McLean, L. Inorg. Synth. 2007, 32, 149. (5) Krysan, D. J.; Mackenzie, P. B. J. Org. Chem. 1990, 55, (6) Xie, Q.; Arias, F.; Echegoyen, L. J. Am. Chem. Soc. 1993, 115, (7) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, R. F.; Bässler, H.; Porsch, M.; Daub, J. Adv. Mater. 1995, 7, 551. (8) D Andrade, B. W.; Datta, S.; Forrest, S. R.; Djurovich, P.; Polikarpov, E.; Thompson, M. E. Org. Electron. 2005, 6, 11. (9) Iwamoto, T.; Watanabe, Y.; Sakamoto, Y.; Suzuki, T.; Yamago, S. J. Am. Chem. Soc. 2011, 133, (10) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02.; Gaussian Inc: Wallingford CT, (11) Becke, A. D. J. Chem. Phys. 1993, 98, (12) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B. 1988, 37, 785. (13) Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab initio Molecular Orbital Theory; John Wiley: New York, S7 --

8 OMe MeO SnMe 3 MeO SnMe 3 OMe 1a' Figure S4. 1 H NMR spectrum of 1a. OMe MeO SnMe 3 MeO SnMe 3 OMe 1a' Figure S5. 13 C NMR spectrum of 1a. S8 --

9 MeO OMe MeO 3a OMe Figure S6. 1 H NMR spectrum of 3a. MeO OMe MeO OMe 3a Figure S7. 13 C NMR spectrum of 3a. S9 --

10 OTBS Br 5d Figure S8. 1 H NMR spectrum of 5d. OTBS 5d Br Figure S9. 13 C NMR spectrum of 5d. S10 --

11 OH Br 5e Figure S10. 1 H NMR spectrum of 5e. OH 5e Br Figure S C NMR spectrum of 5e. S11 --

12 Br Br 1c Figure S12. 1 H NMR spectrum of 1c. Br Br 1c Figure S C NMR spectrum of 1c. S12 --

13 3c Figure S14. 1 H NMR spectrum of 3c. 3c Figure S C NMR spectrum of 3c. S13 --

14 HO OH HO 3b OH Figure S16. 1 H NMR spectrum of 3b. HO OH HO OH 3b Figure S C NMR spectrum of 3b. S14 --

15 [5]CPP Figure S18. 1 H NMR spectrum of [5]CPP. [5]CPP Figure S C NMR spectrum of [5]CPP. S15 --

16 (a) Observed spectrum (b) Observed spectrum (expanded) (c) Simulated spectrum (Calculated for [C 30 H 20 ] + ) Figure S20. MALDI-TOF mass spectrum of [5]CPP. S16 --