Supplementary Figures

Transcription

1 Supplementary Information Bottom-up synthesis of finite models of helical (n,m)-single-wall carbon nanotubes Shunpei Hitosugi, Waka Nakanishi, Takashi Yamasaki and Hiroyuki Isobe* Department of Chemistry, Tohoku University, Aoba-ku, Sendai , Japan * Supplementary Figures Supplementary Figure S1. Molecular structure of Pt-complex 3 determined by X-ray crystallographic analysis of a single crystal obtained from a toluene solution. A representative structure from two geometries is shown with ring-fillings for chrysenylene units. Carbon atoms are colored in gray and Pt atoms are in blue. Hydrogen atoms and solvent molecules are omitted for clarity. The crystallographic data can be obtained free of charge from Cambridge Crystallographic Data Centre (CCDC83362). S1

2 a fr. #1 (A,B,C) fr. #2 (D,E) fr. #3 (F) hours b D E hours c A B C Supplementary Figure S2. HPLC charts for the isolation of [4]CC isomers. (a) A chart of the first HPLC to give three fractions. (b) A chart of the second HPLC of the fraction #2. (c) A chart of the second HPLC of the fraction #1. hours S2

3 (P)-(12,8)-[4]CC (F) (M)-(12,8)-[4]CC (D) (P)-(11,9)-[4]CC (E) (M)-(11,9)-[4]CC (B) (1,1)-[4]CC AABB (A) (1,1)-[4]CC ABAB (C) Supplementary Figure S3. 1 H NMR spectra of isomers (4 MHz, CDCl 3 ). S3

4 (P)-(12,8)-[4]CC (F) 1 MHz (M)-(12,8)-[4]CC (D) 1 MHz (P)-(11,9)-[4]CC (E) 15 MHz (P)-(11,9)-[4]CC (E) 1 MHz (M)-(11,9)-[4]CC (B) 1 MHz (1,1)-[4]CC AABB (A) 1 MHz (1,1)-[4]CC ABAB (C) 1 MHz Supplementary Figure S4. Aromatic resonance of 13 C NMR spectra (CDCl 3 ). S4

5 1 5 cm 1 M 1 2.! (P)-(12,8)-[4]CC (F) cm 1 M nm! (M)-(12,8)-[4]CC (D) cm 1 M nm! (P)-(11,9)-[4]CC (E) cm 1 M nm! (M)-(11,9)-[4]CC (B) cm 1 M nm! (1,1) AABB -[4]CC (A) cm 1 M nm! (1,1) ABAB -[4]CC (C) nm Wavelength Supplementary Figure S5. UV-vis spectra of [4]CC isomers in chloroform. Concentrations are as follows: (P)-(12,8)-[4]CC (F) = 1.7! 1 6 M, (M)-(12,8)-[4]CC (D) = 2.9! 1 6 M, (P)-(11,9)-[4]CC (E) = 1.6! 1 6 M, (M)-(11,9)-[4]CC (B) = 2.9! 1 6 M, (1,1)-[4]CC AABB (A) = 2.2! 1 6 M, (1,1)-[4]CC ABAB (C) = 2.3! 1 6 M. S5

6 a M -1 cm !" -5-1 M -1 cm !" (M)-(12,8)-[4]CC (D) (P)-(12,8)-[4]CC (F) (M)-(11,9)-[4]CC (B) (P)-(11,9)-[4]CC (E) 6 nm 6 nm b M -1 cm (P)-(12,8)-[4]CC (F) 1-4 esu 2 cm 2 4 2!" nm R vel -2-1 M -1 cm !" (P)-(11,9)-[4]CC (E) esu 2 cm nm 1 R vel -1-2 Supplementary Figure S6. CD spectra of [4]CC isomers in chloroform. Overlaid spectra are shown in Fig. 3. (a) Experimental spectra of (12,8)- and (11,9)-[4]CC. Concentrations are as follows: (P)-(12,8)-[4]CC (F) = 3.8! 1 6 M, (M)-(12,8)-[4]CC (D) = 5.! 1 6 M, (P)-(11,9)-[4]CC (E) = 4.! 1 6 M, (M)-(11,9)-[4]CC (B) = 4.6! 1 6 M. (b) Theoretical spectra of (P)-(12,8)- and (P)-(11,9)-[4]CC with methyl substituents. S6

7 (P)-(12,8)-[4]CC HOMO LUMO (P)-(11,9)-[4]CC HOMO LUMO Supplementary Figure S7. Frontier Kohn-Sham orbitals of (P)-helical [4]CC isomers. S7

8 (1,1)-[4]CC AABB (A) (M)-(11,9)-[4]CC (B) (1,1)-[4]CC ABAB (C) (M)-(12,8)-[4]CC (D) (P)-(11,9)-[4]CC (E) (P)-(12,8)-[4]CC (F) UV detector 3 CD detector min min 3 4 Supplementary Figure S8. HPLC analysis of [4]CC obtained in the presence of cholesteryl stearate. The top chart shows the analysis with UV-vis detection at 3 nm, and the bottom chart shows the simultaneous analysis with CD detection at 42 nm. Peaks with positive CD are shown in blue, and those with negative CD are in red. S8

9 Supplementary Tables Supplementary Table S1. Cartesian coordinate of methyl substituted (P)-(12,8)-[4]CC SCF Done: E(RB3LYP) = A.U. after 13 cycles Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S9

10 S1

11 S11

12 S12

13 Supplementary Table S2. Cartesian coordinate of methyl substituted (P)-(11,9)-[4]CC SCF Done: E(RB3LYP) = A.U. after 14 cycles Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S13

14 S14

15 S15

16 S16

17 Supplementary Methods General. Flash silica gel column chromatography was performed on silica gel 6N (spherical and neutral gel, 4-14!m, Kanto). IR spectra were recorded on Thermo Scientific Nicolet is1 FT-IR equipped with an attenuated total reflection (ATR; neat), and were reported as wavenumbers (") in cm 1. Proton ( 1 H) and carbon ( 13 C) nuclear magnetic resonance (NMR) spectra were recorded on JEOL LA 4 ( 1 H: 4 MHz; 13 C: 1 MHz), ECA 6 ( 13 C: 15 MHz) or Bruker AVANCE 4 ( 1 H: 4 MHz; 13 C: 1 MHz) spectrometers. Time-of-flight (TOF) mass spectra were obtained on a JEOL JMS-T1 instrument using Direct Analysis in Real Time (DART) ionization or on a Shimadzu Biotech AXIMA-CFR Plus instrument using Matrix Assisted Laser Desorption Ionization (MALDI) with tetracyanoquinodimethane as the matrix (ca. 5 weight%). The melting points were determined on an IA91 MK3 instrument (Electrothermal Engineering) and were uncorrected. Diffraction analysis of single crystals with X-ray was carried out on a Bruker APEX II CCD diffractometer with graphite-monochromated Mo#$ radiation (! =.7173) at 1 K. UV-visible absorption spectra were recorded with V-67 spectrometer (JASCO). Circular dichroism (CD) spectra were obtained on a spectropolarimeter (JASCO, J-82). Materials. 1,1,1,3,3,3-Hexafluoro-2-propanol (hexafluoroisopropanol, HFIP) was obtained from Central Glass and used without purification. Anhydrous THF (stabilizer free, Wako) and toluene (Kanto) were purified by a solvent purification system (GlassContour) equipped with columns of activated alumina and supported copper catalyst (Q-5). Other solvents were purified by distillation and dried over 4-Å molecular sieves. Butyllithium in hexane was purchased from Kanto and titrated before use. Magic acid and 2,2,2-trifluoroethyl toluenesulfonate were obtained from Aldrich, and borane-thf complex from Kanto. Dichloro(1,5-cyclooctadiene)platinum was prepared as reported 35. Choresteryl stearate was purchased from Wako and purified by silica gel column chromatography. S17

18 Synthesis of 2,8-dibromo-6,12-dihexylchrysene 1 Br hex BH hex 3 THF (.33 eq.) BR 3 R = THF, C to rt 3 h Br hex = n-hexyl CF 3 CH 2 OTs 1) n-buli (2.1 eq.) THF, 78 C 1 min 2) BR 3 (1.1 eq.) 78 C 2 min, reflux 3 h 3) Br 2 (3. eq.) 78 C 1 h Br hex CF 2 4 hex Br FSO 3 H SbF 5 1:1 (2.5 eq.) (CF 3 ) 2 CHOH rt 26 h Br hex 1 21% (2 steps) hex Br We synthesized dibromochrysene 1 by the method that we reported previously for the synthesis of methyl-substituted congeners: To a solution of 2,2,2-trifluoroethyltoluenesulfonate (8.5 g, 33.6 mmol) in THF (16 ml) was added n-butyllithium (1.61 M in hexane, 44.5 ml, 71.7 mmol) at 78 C over 1 min under nitrogen and stirred for 1 min. Tris[2-(3-bromophenyl)octyl]borane was separately prepared by adding borane-thf complex in THF (1.6 M, 39.4 ml, 37. mmol) to a solution of 2-(3-bromophenyl)-1-octene (29.8 g, 112 mmol) in THF (37 ml). The mixture was transferred to a solution of difluorovinyl lithium at 78 C. After being stirred for 3 min, the mixture was heated at reflux for 3 h. The mixture was then cooled to 78 C, and bromine (5.2 ml, 12 mmol) in dichloromethane (34 ml) was added dropwise. The mixture was stirred at 78 C for 1 h, and an aqueous solution of.1 M Na 2 S 2 O 3 (ca. 1 ml) was added. Organic materials were extracted with diethyl ether (3! 2 ml). The organic layer was washed with brine, dried over magnesium sulfate, and concentrated in vacuo. The crude material was purified by silica gel column chromatography (eluent: hexane) to afford difluoroalkene 4 as a colorless oil with a small amount of contaminants (19.1 g). A mixture of diflouroalkene 4 and FSO 3 H SbF 5 (9.58 mg, 79.8 mmol) in HFIP (34 ml) was then stirred at ambient temperature for 26 h. To the mixture was added a saturated aqueous solution of NaHCO 3 (ca. 2 ml). The organic solvent, HFIP, was recovered by distillation, and crude materials were obtained as a residual solid. The residue was dissolved in chloroform (4 ml) and washed with brine, dried over magnesium sulfate, and concentrated in vacuo. Polar byproducts were removed by column chromatography (silica gel: 2 g), and the title product 1 was obtained in 21% yield (2 steps) as a pale yellow solid (3.92 g, 7.7 mmol) after subsequent recrystallization from hexane. Physical data for the characterization Compound 4 (meso : dl = 1:1). IR (neat) 666 (w), 72 (m), 787 (s), 885 (m), 897 (m), 996 (w), 171 (w), 1474 (m), 1558 (m), 1591 (w), 2856 (m), 2928 (m), 2955 (m) cm -1 ; 1 H NMR (4 MHz, S18

19 CDCl 3 ) %.85 (t, J = 7.2 Hz, 6H!2), (m, 4H!2), (m, 8H!2), (m, 8H!2), (m, 4H!2), (m, 2H!2), 7.1 (d, J = 7.6 Hz, 2H), 7.2 (d, J = 7.6 Hz, 2H), 7.14 (dd, J = 7.6, 7.6 Hz, 2H), 7.15 (dd, J = 7.6, 7.6 Hz, 2H), 7.22 (dd, J = 2. Hz, 2H), 7.24 (dd, J = 1.6 Hz, 2H), (m, 2H!2); 13 C NMR (1 MHz, CDCl 3 ) % 14.2, 14.3, 22.7, 22.8, 27.5, 27.5, 29.4, 29.4, 31.7, 31.8, 33.3 (overlapped), 36., 36.2, 44. (t, J CF = 2.4 Hz), 44. (t, J CF = 2.4 Hz), 86.2 (t, J CF = 17 Hz), 86.2 (t, J CF = 17 Hz), 122.6, 122.6, 126.3, 126.3, 129.5, 129.5, 13., 13., 13.6, 13.7, 147.4, 147.5, (t, J CF = 283 Hz) (overlapped); HRMS (DART-TOF) calcd for C 3 H 4 Br 2 F [M-F] , found Compound 1. mp C; IR (neat) 611 (w), 728 (w), 771 (w), 81 (s), 82 (s), 873 (s), 881 (s), 187 (w), 1214 (w), 1281 (w), 1373 (w), 1429 (m), 1465 (m), 158 (m), 1595 (m), 285 (m), 2923 (m), 2955 (m) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.92 (t, J = 7.2 Hz, 6H), (m, 8H), 1.52 (tt, J = 7.2, 7.2 Hz, 4H), 1.85 (tt, J = 7.2, 7.2 Hz, 4H), 3.18 (t, J = 7.2 Hz, 4H), 7.76 (dd, J = 8.8, 2. Hz, 2H), 8.29 (d, J = 2. Hz, 2H), 8.45 (s, 2H), 8.66 (d, J = 8.8 Hz, 2H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 22.8, 29.7, 3.7, 31.9, 34., 121., 121.5, 125.6, 126.8, 127.1, 129.3, 129.4, 132.9, 136.5; HRMS (DART-TOF): m/z calcd for C 3 H 35 Br 2 [M+H] , found Compound 2. mp C; IR (neat) 669 (w), 72 (m), 758 (m), 827 (w), 858 (m), 912 (w), 965 (m), 195 (m), 1142 (s), 1217 (w), 1258 (m), 1295 (m), 134 (m), 1344 (m), 1369 (s), 1466 (w), 1615 (w), 2851 (w), 2929 (w), 2958 (w), 2981(w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.93 (t, J = 7.2 Hz, 6H), (m, 8H), 1.43 (s, 24H), 1.55 (tt, J = 7.6, 7.6 Hz, 4H), 1.91 (tt, J = 7.6, 7.6 Hz, 4H), 3.32 (t, J = 7.6 Hz, 4H), 8.6 (d, J = 8.8 Hz, 2H), 8.54 (s, 2H), 8.67 (s, 2H), 8.81 (d, J = 8.8 Hz, 2H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 22.8, 25.1, 29.6, 3.8, 31.9, 33.9, 84.1, 12.8, 123., 127.6, 13.9, 131.2, 132.3, 132.7, 137.6; HRMS (DART-TOF): m/z calcd for C 42 H 58 B 2 O 4 [M] , found Compound 3. mp C (decomp.); IR (powder) 644 (w), 758 (w), 87 (s), 876 (m), 889 (s), 168 (w), 1179 (w), 1229 (w), 1341 (w), 1364 (w), 1429 (w), 1465 (w), 15 (w), 1578 (w), 2854 (w), 2926 (m), 354 (w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.72 (t, J = 6.4 Hz, 24H), (m, 32H), (m, 16H), (m, 16H), (m, 32H), 3. (t, J = 7.6 Hz, 16H), 5.34 (s, 16H), 7.56 (d, J = 8.8 Hz, 8H), 7.95 (s, 8H), 8.14 (s, 8H), 8.29 (d, J = 8.8 Hz, 8H); 13 C NMR (1 MHz, CDCl 3 ) % 14.2, 22.8, 29.7, 3.2, 3.6, 31.9, 34.4, 14.6, 119.9, 121.8, 126.1, 127.7, 129.8, 131.1, 133.5, 135.6, (P)-(12,8)-[4]CC (F). IR (neat) 7 (w), 726 (w), 743 (w), 811 (s), 871 (m), 174 (w), 1125 (w), 1286(s), 1371 (m), 146 (m), 1585 (w), 1613 (w), 1727 (s), 2855 (m), 2926 (s), 2954 (m), 371 (w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.93 (t, J = 7. Hz, 24H), (m, 32H), (m, 16H), (m, 16H), 2.98 (ddd, J = 14.5, 8.7, 6.5 Hz, 8H), 3.23 (ddd, J = 14.5, 9.1, 5.5 Hz, 8H), 8.9 (dd, J = 9.2, 1.6 Hz, 8H), 8.13 (d, J = 1.6 Hz, 8H), 8.14 (s, 8H), 8.46 (d, J = 9.2 Hz, 8H); S19

20 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 22.8, 29.6, 3.7, 31.9, 33.6, 12.6, 123.2, 123.4, 124.5, 127.2, 129.7, 132., 135.6, 137.1; MS (MALDI-TOF): m/z calcd for C 12 H 136 [M] , found (M)-(12,8)-[4]CC (D). IR (neat) 687 (w), 725 (w), 75 (w), 89 (s), 871 (m), 111 (w), 1172 (w), 1217(w), 1227 (w), 1434 (m), 1463 (m), 1585 (w), 1611 (w), 1739 (m), 2854 (m), 2926 (s), 2952 (m), 375 (w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.93 (t, J = 7. Hz, 24H), (m, 32H), (m, 16H), (m, 16H), 2.97 (ddd, J = 14.5, 8.6, 6.4 Hz, 8H), 3.23 (ddd, J = 14.5, 9., 5.6 Hz, 8H), 8.9 (dd, J = 9.2, 1.6 Hz, 8H), 8.13 (d, J = 1.6 Hz, 8H), 8.14 (s, 8H), 8.46 (d, J = 9.2 Hz, 8H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 22.8, 29.6, 3.7, 31.9, 33.6, 12.6, 123.2, 123.4, 124.5, 127.2, 129.7, 132., 135.6, 137.1; MS (MALDI-TOF): m/z calcd for C 12 H 136 [M] , found (P)-(11,9)-[4]CC (E). IR (neat) 684 (w), 724 (w), 759 (w), 81 (s), 876 (m), 128 (m), 114 (m), 126 (w), 1377 (w), 1429 (w), 1463 (m), 1519 (w), 1594 (w), 1612 (w), 1678 (w), 1727 (w), 2855 (m), 2926 (s), 2953 (m), 374 (w) cm -1 ; (m, 24H), (m, 32H), (m, 16H), (m, 16H), (m, 8H), (m, 8H), 7.84 (dd, J = 9.2, 1.6 Hz, 2H), 7.93 (dd, J = 9.2, 1.6 Hz, 2H), 7.97 (dd, J = 9.2, 1.6 Hz, 2H), 7.98 (dd, J = 9.2, 1.6 Hz, 2H), 8.12 (s, 2H), 8.13 (s, 2H), 8.14 (s, 2H), 8.15 (s, 2H), 8.17 (d, J = 1.6 Hz, 2H), 8.18 (d, J = 1.6 Hz, 2H), 8.21 (d, J = 1.6 Hz, 2H), 8.34 (d, J = 1.6 Hz, 2H), 8.41 (d, J = 9.2 Hz, 2H), 8.42 (d, J = 9.2 Hz, 2H), 8.43 (d, J = 9.2 Hz, 2H), 8.44 (d, J = 9.2 Hz, 2H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 14.3, 14.3, 14.3, 22.8, 22.8, 22.9, 22.9, 29.6 (overlapped), 29.8, 29.9, 3.7, 3.7, 3.9, 31., 31.9 (overlapped), 31.9, 31.9, 33.7 (overlapped), 33.8, 33.9, 12.5 (overlapped 3C), 12.6, 121.5, 122.8, 122.8, 122.9, 124.1, 124.1, 124.4, (overlapped 4C), 125.2, 127.2, 127.2, (overlapped), (overlapped), 129.7, 129.8, 132.1, 132.1, 132.2, 132.3, (overlapped), 136., 136.1, 137., 137.1, 137.1, 137.1; 13 C NMR (15 MHz, CDCl 3 ) % 14.3, 14.3, 14.3, 14.3, 22.8, 22.8, 22.8, 22.9, 29.6 (overlapped), 29.7, 29.9, 3.7, 3.7, 3.9, 31., 31.9 (overlapped), 31.9, 31.9, 33.7, 33.7, 33.8, 33.8, 12.5 (overlapped 3C), 12.6, 121.5, 122.8, 122.8, 122.9, 124.1, 124.1, 124.4, 124.5, 124.5, (overlapped), 125.2, 127.2, 127.2, (overlapped), (overlapped), 129.7, 129.8, 132.1, 132.1, 132.2, 132.3, (overlapped), 136., 136.1, 137., 137.1, 137.1, 137.1; MS (MALDI-TOF): m/z calcd for C 12 H 136 [M] , found (M)-(11,9)-[4]CC (B). IR (neat) 688 (w), 724 (w), 76 (w), 89 (s), 876 (m), 128 (m), 114 (m), 1261 (w), 1377 (w), 1429 (w), 146 (m), 1519 (w), 1595 (w), 1612 (w), 1678 (w), 1715 (w), 2855 (m), 2926 (s), 2953 (m), 374 (w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) % (m, 24H), (m, 32H), (m, 16H), (m, 16H), (m, 8H), (m, 8H), 7.83 (dd, J = 9.2, 1.6 Hz, 2H), 7.93 (dd, J = 9.2, 1.6 Hz, 2H), 7.96 (dd, J = 9.2, 1.6 Hz, 2H), 7.98 (dd, J = 9.2, 1.6 Hz, 2H), 8.12 (s, 2H), 8.13 (s, 2H), 8.14 (s, 2H), 8.15 (s, 2H), 8.17 (d, J = 1.6 Hz, 2H), 8.18 (d, J = 1.6 Hz, 2H), 8.21 (d, J = 1.6 Hz, 2H), 8.34 (d, J = 1.6 Hz, 2H), 8.4 (d, J = 9.2 Hz, S2

21 2H), 8.42 (d, J = 9.2 Hz, 2H), 8.43 (d, J = 9.2 Hz, 2H), 8.44 (d, J = 9.2 Hz, 2H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 14.3, 14.3, 14.3, 22.8, 22.8, 22.9, 22.9, 29.6 (overlapped), 29.8, 29.9, 3.7, 3.7, 3.9, 31., 31.9 (overlapped), 31.9 (overlapped), 33.7 (overlapped), 33.8, 33.9, 12.5 (overlapped 3C), 12.6, 121.5, 122.8, 122.8, 122.9, 124.1, 124.1, 124.4, (overlapped 4C), 125.2, 127.2, 127.2, (overlapped), (overlapped), 129.7, 129.8, 132.1, 132.1, 132.1, 132.3, (overlapped), 136., 136.1, 137., 137.1, 137.1, 137.1; MS (MALDI-TOF): m/z calcd for C 12 H 136 [M] , found (1,1)-[4]CC AABB (A). IR (neat) 684 (w), 725 (w), 759 (w), 81 (s), 876 (m), 126 (m), 115 (m), 1261 (w), 1377 (w), 1428 (w), 1463 (m), 1519 (w), 1594 (w), 1612 (w), 1678 (w), 1717 (w), 2855 (m), 2926 (s), 2953 (m), 375 (w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.89 (t, J = 6.7 Hz, 12H),.92 (t, J = 6.7 Hz, 12H), (m, 32H), (m, 16H), (m, 16H), (m, 8H), (m, 8H), 7.88 (dd, J = 9.2, 1.6 Hz, 4H), 7.9 (dd, J = 9.2, 1.6 Hz, 4H), 8.12 (s, 4H), 8.15 (s, 4H), 8.23 (d, J = 1.6 Hz, 4H), 8.26 (d, J = 1.6 Hz, 4H), 8.41 (d, J = 9.2 Hz, 4H), 8.44 (d, J = 9.2 Hz, 4H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 14.3, 22.8, 22.9, 29.6, 29.7, 3.8, 31., 31.9 (overlapped), 33.7, 33.8, 12.5, 12.5, 122.2, 122.4, (overlapped), 124.7, 125., 127.2, 127.3, 129.7, 129.7, 132.2, 132.2, 136., 136.1, 137., 137.1; MS (MALDI-TOF): m/z calcd for C 12 H 136 [M] , found (1,1)-[4]CC ABAB (C). IR (neat) 757 (w), 81 (s), 877 (m), 129 (m), 195 (m), 1261 (m), 1377 (w), 1428 (w), 1455 (m), 1519 (w), 1596 (w), 1612 (w), 1737 (w), 2854 (m), 2926 (s), 2955 (m), 375(w) cm -1 ; 1 H NMR (4 MHz, CDCl 3 ) %.91 (t, J = 7. Hz, 24H), (m, 32H), (m, 16H), (m, 16H), 3.3 (ddd, J = 14.5, 8.6, 6.6 Hz, 8H), 3.22 (ddd, J = 14.5, 8.7, 5.7 Hz, 8H), 7.85 (dd, J = 9.2, 1.6 Hz, 8H), 8.13 (s, 8H), 8.24 (d, J = 1.6 Hz, 8H), 8.41 (d, J = 9.2 Hz, 8H); 13 C NMR (1 MHz, CDCl 3 ) % 14.3, 22.9, 29.7, 3.9, 31.9, 33.8, 12.5, 122.4, 124.5, 125., 127.2, 129.7, 132.3, 136.3, 137.1; MS (MALDI-TOF): m/z calcd for C 12 H 136 [M] , found Supplementary Reference 35. McDermott, J. X., White, J. F. & Whitesides, G. M. Thermal decomposition of bis(phosphine)platinum(ii) metallocycles. J. Am. Chem. Soc. 98, (1976). S21