Supramolecular ruthenium-alkynyl multicomponent architectures: engineering,

Transcription

1 Electronic supplementary information Supramolecular ruthenium-alkynyl multicomponent architectures: engineering, photophysical properties and responsiveness to nitroaromatics. Rafik Gatri, a,b Ines uerfelli, a,b Mohamed Lofti Efrit, a Françoise Serein-Spirau, c Jean-Pierre Lère-Porte, c Pierre Valvin d, Thierry Roisnel, b Sébastien Bivaud, b Huriye Akdas-Kilig, b Jean- Luc Fillaut, b * a) Laboratoire de Synthèse rganique et Hétérocyclique, Département de Chimie, Faculté des Sciences de Tunis, Campus Universitaire, Université Tunis El Manar 2, 2092 Tunis, Tunisie b) UMR 6226 CNRS - Université Rennes 1, "Institut des Sciences chimiques de Rennes", Avenue du Général Leclerc, Rennes cedex, France c) AM2N UMR 5253 CNRS-Ecole Nationale de Chimie de Montpellier (ENSCM), 8 rue de l Ecole Normale, Montpellier cedex 5, France d) Laboratoire Charles Coulomb UMR 5221 CNRS-UM2, Département Semiconducteurs Matériaux et Capteurs, Université Montpellier 2 Place Eugène Bataillon, Montpellier Cedex 05, France Sections include: General Information and Methods p.2 Experimental Procedures p.3 Absorption and emission spectra of 1b, 3 and 4. p.14 Determination of association constants by NMR studies. p.15 Structural data for complex 3:10. p.18 Decay and Lifetimes. p.46 Detection limit and Selectivity studies p.47 NMR data for intermediates. p.48-1-

2 General Information and Methods Moisture or oxygen sensitive reactions were performed under an inert atmosphere using standard Schlenk techniques with a double manifold vacuum line. Solvents were freed of impurities by usual procedures and stored under argon. All reagents were obtained from commercial sources in 98% or greater purity and used as received. Secondary ion (SI) mass spectra were recorded on a VG ZAB 2SEQ spectrometer (30 kv Cs + ions, current 1 ma, accelerating potential 8 kv, matrix o-nitrophenyloctyl ether or m- nitrobenzylic alcohol) and electron impact (EI), including high-resolution (HR), mass spectra on a VG Autospec instrument (70 ev electron energy, 8 kv accelerating potential) at the Center de Mesures Physiques de l uest, Rennes, France. Microanalyses were carried out at at the Center de Mesures Physiques de l uest, Rennes, France. NMR Spectra: 1 H NMR, 31 P NMR and 13 C NMR spectra were run either on a Bruker DPX 200 MHz spectrometer, a multinuclear Bruker WB 300 MHz spectrometer or a Bruker Avance DRX 500 MHz spectrometer. Chemical shifts are reported in parts per million (ppm) relative to tetramethylsilane (TMS) as the standard for 1 H and 13 C NMR spectra and H 3 P 4 as the standard for 31 P NMR spectra. UV-vis absorption spectra were recorded using a UVIKN 9413 or Biotek Instruments XS spectrophotometer using quartz cuvettes of 1cm path-length. Emission spectra were recorded using a Perkin Elmer LS55 luminescence spectrometer. The spectra in solution were obtained at 20 C using a quartz cuvette with a path length of 1 cm. The absorbance of all samples studied by fluorescence spectroscopy was below 0.1 in order to avoid self absorption. Fluorescence quenching experiments were carried out by microtitration in a thermostated solution placed in a quartz cuvette. The fluorescence spectrum was recorded in the absence of the quencher at 20 C. Then, the spectra were repeatedly acquired after microliter aliquots of concentrated 2,4-dinitrotoluene (DNT) solution to minimize the volume variation of the solution. The solution was magnetically stired after each addition. The concentration of the fluorophore remains constant and the DNT concentration were known for each aliquot. The 2-3 complexes were prepared in the cuvet by mixing solutions of 2 and

3 Experimental Procedures 1.1. Preparation of N-(4-iodophenyl)isocyanuric acid 9 H 2 N HN HN N 2 a H 2 N HN HN I b HN HN N I The N-(4-iodophenyl)isocyanuric acid 9 was obtained from the reaction of 1-(4- iodophenyl)biuret 8 (250 mg, 0.82 mmol) in THF (8 ml) and N,N -carbonyldiimidazole (640 mg, 3.9 mmol). 5.9 ml of a 1M potassium tert-butoxyde solution in THF were added to the solution. The mixture was stirred under argon at 60 C for 24 h. After the solvent was removed in vacuo, 100 ml ethyl acetate and 100 ml 1M HCl were added. The organic phase was washed twice with brine, and dried with sodium sulfate. After removal of the solvent in vacuo, silica gel column chromatography (CH 2 Cl 2 /EtAc; 2/1) was carried out to afford the product 9 as a pale yellow powder (210 mg, 77%). Anal. Calc. for C 9 H 6 IN 3 3 : C, 32.65; H, 1.83; N, Found: C, 32.12; H, 1.61; N, H NMR ( MHz, DMS-d 6, 297 K): δ = (br, 2H, NH), 7.82 (d, J=6.5 Hz, 2H; C 6 H 4 ), 7.16 (d, J=6.5 Hz, 2H; C 6 H 4 ). 13 C NMR (50.32 MHz, DMS-d 6, 300K): δ = 149.6, 148.9, 137.7, 134.2, 131.6, Preparation of 1,4-bis(alkyloxy)-2,5-diethynyl- benzene 6a,b. Alk Alk Br Br Alk Alk a: b: 5a,b Alk = C 8 H 17 Alk = C 12 H 25 6a,b HN HN N Alk Alk N NH NH HN HN N I 1a,b A three-necked flask was equipped with a magnetic stirrer, a condenser and a funnel. To a mixture of 2,5-di(alkyloxy)benzène (30 mmol), sodium acetate trihydrate (60 mmol ) and acetic acid (35 ml), bromine (3.0 ml, 60 mmol) was added dropwise and the mixture -3-

4 allowed to stir at room temperature, overnight. 100 ml ice/water was poured into the solution. The solids were dissolved in dichloromethane and washed with water and then with 5% sodium carbonate, until the aqueous phase remains neutral. The combined organic layer was dried with magnesium sulfate. After removal of the solvent, the crude products were purified by crystallization from pentane to give 5a, b as white powders. 5a (9.50 g, 64%). Anal. Calc. for C 22 H 36 Br 2 2 : C, 53.67; H, Found: C, 53.43; H, H NMR ( MHz, CDCl 3, 297 K): δ = 7.11 (s, 2H; Ar-H), 3.97 (t, J=6.5 Hz, 4H; CH 2 ), 1.79 (m, 4H; CH 2 -CH 2 ), (m, 20H; CH 2 ), 0.91 (t, 6H, J=6.5 Hz; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 147.6, 117.4, 110.9, 68.0, 31.9, 29.6, 29.3, 25.9, 22.6, b (9.97g, 74%). Anal. Calc. for C 30 H 52 Br 2 2 : C, 59.60; H, Found: C, 59.63; H, H NMR ( MHz, CDCl 3, 297 K): δ = 7.11 (s, 2H, Ar-H), 3.93 (t, J=6.4 Hz, 4H; CH 2 ), 1.79 (m, 4H; CH 2 -CH 2 ), (m, 36H; CH 2 ), 0.90 (t, J=6,7 Hz, 6H; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ =147.5, 117.4, 110.9, 68.0, 31.9, 29.7, 29.6, 29.4, 29.3, 29.2, 26.0, 22.7, ,4-bis(trimethylsilylethynyl)-2,5-di(dodecyloxy)benzene was obtained from 5a (3.00 g, 6.09 mmol) in THF (40 ml) and ipr 2 NH (20 ml). Under argon protection, trimethylsilylacetylene (0.95 g, 14 mmol), PdCl 2 (PPh 3 ) 2 (90 mg, 0.13 mmol), and CuI (45 mg, 0.24 mmol) were added to the solution. The mixture was then stirred under argon at 60 C for 16 h. The solvent was then removed in vacuo. The residue was dissolved in Et 2 (50 ml) before being washed with H 2 (2 20 ml) and brine (20 ml). The organic phase was then dried (Na 2 S 4 ). After the solvent was removed in vacuo, column chromatography (Si 2 : pentane/ Et 2 = 97:3) was carried out to provide 1,4-bis(trimethylsilylethynyl)-2,5- di(octyloxy)benzene as a yellow oil (3.05g, 95%). 1 H NMR ( MHz, CDCl 3, 297 K): δ = 6.91 (s, 2H, Ar-H), 3.96 (t, J=6.4 Hz, 4H; CH 2 ), 1.81 (m, 4H; CH 2 -CH 2 ), (m, 20H; CH 2 ), 0.91 (t, 6H; CH 3 ), 0.27 (s, 18H, Si(CH 3 ) 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 151.3, 117.4, 111.2, 106.8, 102.7, 68.1, 31.9, 29.6, 29.3, 25.9, 22.6, 14.1, Similarly, 1,4-bis(trimethylsilylethynyl)-2,5-di(dodecyloxy)benzene was obtained from 5b (3.7 g, 6.09 mmol): (3.66 g, 94 %). 1 H NMR ( MHz, CDCl 3, 297 K): δ = 6.93 (s, 2 H, Ar-H), 3.97 (t, J=6.4 Hz, 4 H; CH 2 ), 1.79 (m, 4 H; CH 2 CH 2 ), (m, 36 H; - (CH 2 )-), 0.88 (t, J=6.4 Hz, 6 H; CH 3 ), 0.28 (s, 18H, Si(CH 3 ) 3 ). 13 C NMR (50.32 MHz, CDCl 3, -4-

5 300K): δ = 153.9, 117.7, 113.2, 107.8, 103.6, 69.6, 31.9, 29.7, 29.6, 29.4, 29.2, 29.1, 25.9, 22.7, 14.0, ,4-bis(octyloxy)-2,5-diethynyl-benzene 6a: 1,4-bis(trimethylsilylethynyl)-2,5- di(octyloxy)benzene (3.06 g, 5.81 mmol) was dissolved in a mixture of MeH (30 ml) and THF (10 ml). The reaction mixture was purged with argon flow for 15min ml of a 2.5 N NaH solution was added. The mixture was stirred at room temperature for 5h. The solvents were removed in vacuo. The residue was then dissolved in CH 2 Cl 2 (5 ml) before being washed with H 2 (2 3 ml) and brine (3 ml), and dried (Na 2 S 4 ). After the solvent was removed in vacuo, column chromatography (Si 2 : CH 2 Cl 2 ) was carried out to afford the product 6a as a yellowish solid (2.22 g, 89%). Anal. Calc. for C 26 H 38 2 : C, 81.61; H, Found: C, 81.59; H, H NMR ( MHz, CDCl 3, 297 K): δ = 6.94 (s, 2H; Ar-H), 3.97 (t, J=6.6Hz, 4H; CH 2 ), 3.35 (s, 2H; CH), 1.79 (m, 4H; CH 2 -CH 2 ), (m, 20H; CH 2 ), 0.91 (t, J=5.1Hz, 6H; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 151.3, 117.4, 109.2, 81.9, 78.7, 68.1, 31.9, 29.7, 29.3, 25.9, 22.6, ,4-bis(dodecyloxy)-2,5-diethynyl-benzene 6b: 1,4-bis(trimethylsilylethynyl)-2,5- di(dodecyloxy)benzene (1.06 g, 1.66 mmol) was dissolved in THF (15 ml). The reaction mixture was purged with argon flow for 15min ml of tetra n-butylammonium fluoride, 1M solution in THF was added. The mixture was stirred at room temperature for 2h. The solvent was removed in vacuo. The residue was then dissolved in Et 2 (50 ml) before being washed with H 2 (2 30 ml) and brine (30 ml). The organic phase was then dried (Na 2 S 4 ). After the solvent was removed in vacuo, column chromatography (Si 2 : pentane/ch 2 Cl 2 9/1) was carried out to afford the product 6b as a yellow solid (624 mg, 77%). Anal. Calc. for C 34 H 54 2 : C, 82.53; H, Found: C, 82.12; H, H NMR ( MHz, CDCl 3, 297 K): δ = 6.96 (s, 2 H), 3.98 (t, J=6.4 Hz, 4 H; CH 2 ), 3.34 (s, 2 H; CH), 1.79 (m, 4 H; CH 2 CH 2 ), (m, 36 H; CH 2 ), 0.9 (t, J=6.4Hz, 6 H; CH 3 ); 13 C NMR (50.32 MHz, CDCl 3, 300K): δ =153.8, 117.8, 113.2, 82.4, 79.8, 69.7, 31.9, 29.7, 29.6, 29.3, 29.2, 29.1, 25.9, 22.8,

6 2.6. Preparation of 1a,b 1a: Under argon protection, N-(4-iodophenyl) isocyanuric acid 9 (477 mg, 1.44 mmol), and 6a (250 mg, 0.65 mmol) were dissolved in THF (20 ml). PdCl 2 (PPh 3 ) 2 (38 mg, 54 µmol), CuI (20 mg, 0.1 mmol) and distilled NEt 3 (5 ml) were added to the solution. The mixture was then stirred at room temperature for 72h. The solvent was then removed in vacuo. The residue was washed several times with CH 2 Cl 2 and ethyl acetate, giving rise to a yellow solid, hardly soluble in hot THF and DMS but not soluble enough to allow purification and characterization. 1b was obtained from 6b (400 mg, mmol), 590 mg (1.78 mmol) N-(4-iodophenyl) isocyanuric acid 9, PdCl 2 (PPh 3 ) 2 (57 mg, 81 µmol), CuI (20 mg, 0.1 mmol) and PPh 3 (50 mg, 0.19 mmol) in anhydrous THF (10 ml) and distilled NEt 3 (10 ml). The mixture was then stirred under argon at room temperature for 72 h. The solvent was then removed in vacuo. The residue was flash chromatographed on silica gel eluting successively with dichloromethane and tetrahydrofuran which provides 1b as a yellow solid, which was further purified by crystallisation from hot methanol (328 mg, 45%). Anal. Calc. for C 52 H 64 N 6 8 : C, 69.31; H, Found: C, 69.21; H, H NMR ( MHz, DMS-d 6, 297 K): δ = (br, 4H; NH), 7.57 (d, J=8 Hz, 4H; C 6 H 4 ), 7.38 (d, J=8 Hz, 4H; C 6 H 4 ), 7.19 (s, 2H; C 6 H 2 ), 4.06 (t, J=6.4 Hz, 4 H; CH 2 ), 1.49 (m, 4 H; CH 2 CH 2 ), (m, 36H; CH 2 ), 0.81 (t, J=6.4 Hz, 6 H; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 154.4, 149.6, 148.7, 134.7, 131.8, 129.6, 124.2, 117.2, 114.4, 94.2, 87.3, 69.7, 32.4, 30.2, 29.9, 29.7, 29.6, 29.5, 25.4, 23.1, Preparation of 11 C 8 H 17 C 8 H 17 Br C 8 H 17 C 8 H C 8 H 17 C 8 H 17 N NH NH HN HN N I

7 3.1. Bromo-2,5-dioctyloxybenzene 12 was obtained from the reaction of 2- bromohydroquinone (2.0 g, 10.6 mmol), K 2 C 3 (4.0 g, 29 mmol), and 1-octyl bromide (3.7 ml, 22.3 mmol) in 2-butanone (15 ml). The reaction mixture was stirred at reflux for 24 h, under argon. After cooling, the solvent was removed in vacuo. The residue was washed with water, before being dissolved in CH 2 Cl 2 (50 ml). This organic phase was washed with a 1N NaH solution and several times with water, before being dried (Na 2 S 4 ). Removing of the solvent afforded 12 (3.71 g, 84%) as a brownish oil. 1 H NMR ( MHz, CDCl 3, 297 K): δ =7.13 (d, J=2.3 Hz, 1H; C 6 H 3 ), (m, 2H; C 6 H 3 ), 3.94 (m, 4 H; CH 2 ), 1.83 (m, 4 H; CH 2 CH 2 ), (m, 20H; -(CH 2 )-), 0.92 (t, J=6.8 Hz, 6 H; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 151.6, 150.9, 123.4, 121.5, 115.7, 108.8, 72.1, 71.2, 31.9, 29.3, 29.2, 29.1, 26.0, 23.0, Ethynyl-2,5-dioctyloxybenzene 13. Bromo-2,5-dioctyloxybenzene 12 (200 mg, mmol), Pd(PPh 3 ) 2 Cl 2 (10 mg, mmol), PPh 3 (10.0 mg, 0.04 mmol) and CuI (3 mg, 0.16 mmol) were added to a degassed solution of triethylamine (15 ml) and THF (5 ml). Trimethylsilylacetylene (70 mg, 0.7 mmol) was added dropwise to the suspension. The reaction mixture was stirred at reflux for 70 h. After cooling, the solvent was removed under reduced pressure, and the residue was filtered over a short silica gel column with ether as eluent. A dark yellow oil was obtained, whose 1 H NMR spectrum corresponds to 2,5-dioctyloxy-4-trimethylsilylethynylbenzene. This compound was used without further purification for the next step. 1 H NMR ( MHz, CDCl 3, 297 K): δ = 7.01 (d, J=2.7Hz, 1H), (m, 2H; C 6 H 3 ), 3.95 (m, 4H; CH 2 ), 1.80 (m, 4H; CH 2 - CH 2 ), (m, 20H; CH 2 ), 0.91 (t, J=6.8Hz, 6 H; CH 3 ), 0.08 (Si(CH 3 ) 3 ). Tetra n-butyl ammonium fluoride (0.6 ml 1N solution in THF) was added at room temperature to a stirred solution of 2,5-dioctyloxy-4 trimethylsilylethynylbenzaldehyde (150 mg, 0.58 mmol) in 5 ml of THF. The reaction mixture was stirred 2 h at room temperature, under argon. The solvent was removed in vacuo, and the residue was chromatographed on a silica gel column with a n-pentane/et 2 mixture (95/5 vol/vol) as eluent. 1-Ethynyl-2,5- dioctyloxybenzene was thus obtained as a yellow oil. Anal. Calc. for C 24 H 38 2 : C, 80.39; H, Found: C, 79.87; H, H NMR ( MHz, CDCl 3, 297 K): δ = 7.01 (d, J=2.7Hz, 1H), (m, 2H; C 6 H 3 ), 3.95 (m, 4H; CH 2 ), 3.26 (s, 1H), (m, 4H; CH 2 -CH 2 ), (m, 20H; CH 2 ), 0.91 (J=6.8 Hz, 6 H; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ =154.6, 152.6, 117.0,113.9, 112.3, 80.8, 80.1, 71.1, 70.2, 31.9, 29.3, 29.2, 29.1, 26.0, 23.0,

8 3.2. 2,5-di(octyloxy)benzene-1-ethynyl-[4-phenyl (isocyanuric acid)] 11 was obtained from 13 (120 mg, mmol), 122 mg (0.37 mmol) N-(4-iodophenyl) isocyanuric acid 9, PdCl 2 (PPh 3 ) 2 (25 mg, 36 µmol), CuI (100 mg, 0.05 mmol) and PPh 3 (25 mg, mmol) in anhydrous THF (50 ml) and distilled NEt 3 (5 ml). The mixture was then stirred under ar at room temperature for 72 h. The solvent was then removed in vacuo. The residue was flash chromatographed on a silica gel column with dichloromethane and diethyl ether (5/1) which provides 11 as a yellow solid (132 mg, 70%). Anal. Calc. for C 33 H 43 N 3 5 : C, 70.56; H, 7.72; N, Found: C, 70.12; H, 8.01; N, m/z (ESI) , ([M+Na] +, C 33 H 43 N 3 5 Na requires ). 1 H NMR ( MHz, CDCl 3, 297 K): δ = (2H, NH), 7.65 (2H, d, J=8.5Hz, C 6 H 4 ), 7.28 (2H, d, J=8.5Hz, C 6 H 4 ), 7.05 (1H, s, C 6 H 3 ), 6.89 (2H, m, C 6 H 3 ), 4.03 (4H, m; CH 2 ), 1.79 (4H, m; CH 2 -CH 2 ), (20 H, m; CH 2 ), 0.92 (6H, m; CH 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 154.5, 151.1, 148.5, 146.3, 134.0, 132.7, 121.1, 119.2, 116.5, 114.8, 114.2, 108.2, 88.8, 79.2, 68.6, 68.1, 31.9, 29.3, 29.2, 29.1, 26.0, 23.0, Preparation of 10 HN HN N I HN HN N was obtained from 122 mg (0.37 mmol) N-(4-iodophenyl) isocyanuric acid 9, phenylacetylene (0.4 mmol, 41 mg), PdCl 2 (PPh 3 ) 2 (25 mg, 36 µmol), CuI (100 mg, 0.05 mmol) and PPh 3 (25 mg, mmol) in anhydrous THF (50 ml) and distilled NEt 3 (5 ml). The mixture was then stirred under Ar at room temperature for 72 h. The reaction mixture was filtrated over a short silica gel column with THF as eluent. After removal of the solvent, the residue was washed several times with CH 2 Cl 2. Anal. Calc. for C 17 H 11 N 3 3 3/2CH 2 Cl 2 : C, 58.63; H, 3.43; N, Found: C, 59.12; H, 3.61; N, m/z (ESI) , ([M+Na] +, C 17 H 11 N 3 3 Na requires ). 1 H NMR ( MHz, DMS-d 6, 297 K): δ =11.53 (s, 2H, -NH), 7.65 (d, 2H, CH), 7.64 (d, 2H, CH) ; 7.44 (m, 4H, CH) ; 7.40 (m, 2H, CH). 13 C NMR (50.32 MHz, DMS-d 6, 300K): δ =150.3, 149.3, 137.8, 132.2, 131.9, 130.2, 129.4, 129.2, 122.9, 122.5, 90.4,

9 4. Preparation of 2 C 8 H 17 C8 H C 8 H 17 C 8 H Br a b C 8 H 17 Br Br C 8 H 17 C 8 H 17 5a C 8 H 17 C 8 H 17 C8 H 17 Br HN HN N I C 8 H 17 C8 H 17 C 8 H 17 c 9 16 C 8 H 17 C 8 H 17 C8 H 17 HN H N N d C 8 H 17 C 8 H 17 C 8 H 17 C 8 H 17 2 C 8 H 17 C8 H 17 N NH N H 4.1 Preparation of 15. t-buk (1.15g, 1.3 mmol) was added to the solution of (7-bromo-9,9- dioctyl-9h-fluoren-2-yl)methyl-diethylphosphonate (710 mg, 1.1 mmol) and 2,5- octyloxyterephtalaldehyde (200 mg, 0.5 mmol) in THF (20 ml) at 0 C. The mixture was stirred overnight. The solution was filtered and the solid washed with THF. Solvent was removed. The residue was flash chromatographed on a silica gel column with pentane, which provides 15 as a yellow solid (430 mg, 30%). Anal. Calc. for C 84 H 120 Br 2 2 : C, 76.84; H, Found: C, 76.34; H, H NMR ( MHz, CDCl 3, 297 K): δ = 7.57 (d, J=8.1 Hz, 2H; ArH), 7.46 (br. s, 4H; ArH + CH=), 7.38 (br. s, 6H; ArH), 7.19 (br. s, 4H; ArH), 7.11 (s, 2H), 4.10 (t, J=6.2 Hz, 4H; -CH 2 ), 1.94 (m, 8H, CH 2 ), (m, 64H, -CH 2 -), 0.81 (t, J=6.6 Hz, 18H, CH 3 ), 0.62 (m, 8H, -CH 2 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ =153.2, 151.1, 150.8, 139.9, 139.6, 129.9, 129.2, 126.9, 126.1, 125.5, 123.0, 122.0, 120.9, 119.9, 110.5, 69.5, 55.3, 40.4, 31.9, 31.8, 30.0, 29.7, 29.5, 29.4, 29.3, 29.2, 26.4, 23.7, 22.7, 22.6, 14.1,

10 4.2. Preparation of 16: 15 (200 mg, mmol), Pd(PPh 3 ) 2 Cl 2 (10 mg, mmol), PPh 3 (10.0 mg, 0.04 mmol) and CuI (3 mg, mmol) were added to a degassed solution of triethylamine (15 ml) and THF (5 ml). Trimethylsilylacetylene (90 mg, 0.9 mmol) was added slowly and dropwise to the suspension. The reaction mixture was then stirred at reflux for 70 h. After cooling, the solvent was removed under reduced pressure, and the residue was filtered over a short silica gel column with ether as eluent. A dark yellow oil was obtained which was used without further purification for the next step. 1 H NMR ( MHz, CDCl 3, 297 K): δ = 7.68 (d, J=7.9Hz, 2H), (m, 10H), 7.46 (br. s., 2H), 7.27 (d, J=16.4Hz, 2H), 7.21 (br. s., 2H), 4.12 (t, 4H; CH 2 ), 2.00 (m, 4H; CH 2 -CH 2 ), (m, 32H; CH 2 ), 0.91 (t, J=6.8 Hz, 6 H; CH 3 ), 0.85 (t, J=7.2 Hz, 12 H; CH 3 ), 0.62 (m, 8H), 0.08 (Si(CH 3 ) 3 ). Tetra n-butyl ammonium fluoride (0.9 ml 1N solution in THF) was added at room temperature to a stirred solution of this oil (120 mg, mmol) in 5 ml of THF. The reaction mixture was stirred 18 h at room temperature, under argon. The solvent was removed in vacuo, and the residue was chromatographed on a silica gel column with a n-pentane/ CH 2 Cl 2 mixture (90/10 vol/vol) as eluent. 16 was obtained as a yellow powder (140 mg, 71%). Anal. Calc. for C 88 H : C, 87.21; H, Found: C, 87.87; H, H NMR ( MHz, CDCl 3, 297 K): δ = 7.70 (d, J=8.1Hz, 2H), 7.66 (d, J=8.1Hz, 2H), (m., 6H), 7.52 and 7.51 (d, 2 x 1H), 7.50 (br. s., 2H), 7.29 (br. s., 2H), 7.27 (d, J=16.5Hz, 2H), 7.21 (s, 2H), 4.13 (t, 4H; CH 2 ), 3.18 (s, 2H, CH), 2.03 (m, 4H; CH 2 -CH 2 ), (m, 68H; CH 2 ), 0.94 (t, J=6.8Hz, 6 H; CH 3 ), 0.85 (t, J=7.2 Hz, 12 H; CH 3 ), 0.65 (m, 8H; CH 2 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ =151.6, 151.2, 151.0, 141.7, 139.9, 137.6, 131.2, 129.3, 127.0, 126,5, 125.5, 123.2, 121.0, 120.3, 120.0, 119.5, 110.6, 84.8, 69.6, 40.4, 31.9, 31.8, 30.1, 29.7, 29.6, 29.5, 29.4, 29.3, 26.4, 23.8, 22.7, 22.6, 14.2, was obtained from 16 (60 mg, 49 µmol), 50 mg (147 µmol) N-(4-iodophenyl) isocyanuric acid 9, PdCl 2 (PPh 3 ) 2 (4 mg, 4.41 µmol), CuI (1.5 mg, 7.84 µmol) and PPh 3 (1.5 mg, 5.39 µmol) in anhydrous THF (10 ml) and distilled NEt 3 (10 ml). The mixture was stirred at room temperature for 4 days. After removal of the solvent, 2 was dissolved in dichloromethane and purified by filtration on Celite (55 mg, 70%). Anal. Calc. for C 106 H N 6 : C, 78.65; H, 8.22; N, Found: C, 77.97; H, 8.34; N, H NMR ( MHz, DMS-d 6, 297 K): δ = (br, 4H; NH), 7.69 (d, J=8.1Hz, 2H), (m, 10H; aromatics), 7.51and 7.50 (d, 2 x 1H), 7.48 (br. s., 2H), 7.29 (br. s., 2H), 7.26(d, -10-

11 J=16.0Hz, 2H), 7.21 (s, 2H), 4.14 (t, 4H; CH 2 ), 2.05 (m, 4H; CH 2 -CH 2 ), (m, 68H; -(CH 2 )-), 0.94 (t, J=6.8Hz, 6 H; CH 3 ), 0.85 (t, J=7.2 Hz, 12 H; CH 3 ), 0.66 (m, 8H). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ =151.5, 151.1, 151.0, 149.7, 148.6, 141.7, 139.9, 137.7, 134.8, 131.8, 131.1, 129.7, 129.5, 127.0, 126.5, 125.3, 124.2, 123.1, 121.0, 120.5, 120.3, 119.7, 110.7, 94.9, 87.4, 69.6, 40.5, 31.8, 31.7, 30.1, 29.8, 29.7, 29.5, 29.3, 29.2, 26.4, 23.8, 22.9, 22.7, 14.2, H 2 N N NH 17 a I NH N N H b, c H NH N N H I CCl NH N NH NH N NH CCl d, f d, e N H N HN Ph 2 P PPh 2 NH N N H Ph 2 P PPh 2 NH N N H Ru Cl Ru HN N HN Ph 2 P PPh 2 Ph 2 P NH PPh 2 N NH 4 3 NH N NH iodo-isophthaloyl chloride Iodo-isophthalic acid, (2 g, 6.84 mmol) prepared according to the literature, [1] was slowly added to thionyl chloride (8 ml, mmol), under argon. This mixture was then stirred at reflux for 6 h. After cooling, the solvent was removed by distillation, and the viscous residue was dried under vacuum overnight. 18 was used without further purification for the next step. 1 H NMR ( MHz, CDCl 3, 297 K): δ = 8.87 (t, J=1.7Hz, 1H ), 8.59 (d, J=1.7Hz, 2H). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 165.8, 145.2, 135.5, 132.6, N-(6-Aminopyridin-2-yl)-3,3-dimethylbutyramide 17 To the solution of 2,6-diaminopyridine (2 g, 18.3 mmol) and triethylamine (2.6 ml, 18.3 mmol) in THF (20 ml), is added (CH 3 ) 3 CCH 2 CCl (1.8 ml, 18.3 mmol) in THF (10 ml) dropwise over 2h, at 0 C, under argon.this mixture is stirred at room temperature for 72 h. -11-

12 Then the mixture is filtered and the solvent removed in vacuo. The residue was flash chromatographed on a silica gel column with dichloromethane and ethyl acetate (4/1) which provides 17 as a white solid (1.74 g, 46%). 1 H NMR ( MHz, CDCl 3, 297 K): δ = 7.77 (br. s., 1H, CNH), 7.55 (d, J=7.9 Hz, 1H ; H py ), 7.42 (dd, J=7.9 Hz, 1H; H py ), 6.23 (dd, J=7.9 Hz, J=0.7 Hz, 1H; H py ), 4.35 (br. s., 2H; NH 2 ), 2.18 (s, 2H; CH 2 C(CH 3 ) 3 ), 1.05 (s, 9H; C(CH 3 ) 3 ). 13 C NMR (50.32 MHz, CDCl 3, 300K): δ = 170.3, 157.1, 149.9, 140.2, 104.2, 103.3, 51.6, 31.3, N,N -Bis[6-(3,3-dimethylbutyrylamino)pyridine-2-yl]-5-iodo-isophthalamide 19 To the mixture of N-(6-aminopyridin-2-yl)-3,3-dimethylbutyramide 17 (2.84 g, 13.7 mmol) and triethylamine (1.9 ml, 13.7 mmol) in THF (40 ml) at 0 C, 5-iodo-isophthaloyldichloride 18 (2.24 g, 6.81 mmol) in THF (40 ml) is added over 1h. The mixture is stirred at 0 C for 3h and at room temperature for 48h. The mixture is filtered, the solid residue is washed with THF. After removal of the solvent under vacuum, 19 is purified by chromatography on a silica gel column with dichloromethane and ethyl acetate (3/1) and obtained as a white powder (3.89, 85%). m/z (ESI) , ([M+Na] +, C 30 H 35 IN 6 4 Na requires ). 1 H NMR ( MHz, CDCl 3, 297 K): δ = 8.67 (br. s., 2H; NH), 8.38 (br. s., 2H; NH), 8.14 (s, 1H), 8.10 (s, 2H), 7.94 (m. 4H), 7.73 (d. J=8.1Hz. 2H), 2.27 (s. 4H; CH 2 C(CH 3 ) 3 ), 1.11 (s. 18H; CH 2 C(CH 3 ) 3 ). 13 C NMR ( MHz, CDCl 3, 300K): δ = 170.4, 163.0, 149.7, 149.6, 140.6, 140.3, 136.2, 125.2, 109.8, 109.0, 94.6, 51.3, 31.2, N,N -Bis[6-(3,3-dimethylbutyrylamino)pyridine-2-yl]-trimethylsilylethynylisophtalamide was obtained from 19 (1 g, 1.49 mmol), PdCl 2 (PPh 3 ) 2 (12 mg, mmol), CuI (4 mg, mmol) and PPh 3 (2 mg, 0.01 mmol) in anhydrous THF (30 ml) and distilled NEt 3 (15 ml). Trimethylsilylacetylene (176 mg, 1.79 mmol) was added slowly and dropwise to the suspension. The reaction mixture was then stirred at room temperature for 48 h. The solvent was removed under reduced pressure, and the yellow solid (890 mg, 93%) was purified by chromatography on a silica gel column with a CH 2 Cl 2 /EtAc 7/1 mixture. m/z (ESI) , ([M+Na] +, C 35 H 44 N 6 4 SiNa requires H NMR ( MHz, CDCl 3, 297 K): δ = 8.63 (br s, 2H, NH), 8.37 (br s, 2H, NH), 8.15 (s, 1H), 8.00 (s, 2H), 7.8 (m, 4H), 7.74 (d, J=8 Hz, 2H), 2.29 (s, 4H, CH 2 C(CH 3 ) 3 ), 1.12 (s, 18H, CH 2 C(CH 3 ) 3 ), 0.3 (s, 9H, Si(CH 3 ) 3 ). 13 C NMR ( MHz, CDCl 3, 300K): δ = 170.4, 163.7, 150.0, 149.3, 140.7, 125.6, 134.0, 125.6, 124.9, 110.0, 109.5, 102.3, 97.7, 51.2, 31.2, 29.5,

13 5.5. Desilylation (500 mg, mmol) was obtained by reaction with KF (68 mg, 11.7 mmol) in MeH (35 ml), at room temperature for 16h. Classical work-up (water, CH 2 Cl 2 ) afforded 20 as a brown powder (430 mg, 97 %). m/z (ESI) , ([M+Na] +, C 32 H 36 N 6 4 Na requires H NMR ( MHz, CDCl 3, 297 K): δ = 8.54 (br, 2H, NH), 8.44 (br, 2H, NH), 8.18 (s, 1H), 8.00 (s, 2H), 7.90 (m, 4H), 7.77 (d, J=8Hz, 2H, C 6 H 3 ), 3.34 (s, 1H, CH), 2.29 (s, 4H, CH 2 C(CH 3 ) 3 ), 1.13 (s, 18H, CH 2 C(CH 3 ) 3 ). 13 C NMR ( MHz, CDCl 3, 300K): δ = 170.4, 163.5, 150.0, 149.3, 140.7, 135.2, 134, 126.1, 123.8, 119.9, 109.4, 81.2, 79.8, 51.3, 31.2, [1] F. Wessendorf and A. Hirsch, Tetrahedron 2008, 64,

14 Figure S1: Absorption spectra of 3 and 4 (3x10-5 M in CH 2 Cl 2 ) at 298 K. Figure S2: Absorption and emission (λ ex =410 nm) spectra of 1b (3x10-5 M in CH 2 Cl 2 ) at 298 K. The absorption spectrum of 4 is indicated for comparison. -14-

15 Determination of association constants by NMR studies. Dilution studies (3.0 mm to 0.1mM) in CDCl 3 revealed weak self-binding for compound 3 at room temperature. Using the non-linear curve fitting procedure, [1]. the Kass of dimerization was calculated to be 50 M -1 for dimer 3. Figure S3 : Part of the 1 H NMR spectrum of 3 in CDCl 3 solution showing the dimerisation induced shift changes (concentrations from bottom to top: 0.095, 0.19, 0.375, 0.75, 1.5, 3 mm). (Right : fit of the chemical shift data for NH ext of 3 ( ) with values ( )calculated for a binding constant K dim of 50 M -1, δ free = 8.0 ppm, δ dim = 8.20ppm. Figure S4 : Self-assembly study between 4 and 11. (0, 0.5, 1.0, 2.0, 3.0 and 6.0 equivalents 11 from bottom to top) Stock solutions were prepared with dissolved 4 (10 mg, 1.0 x10-3 mol) and 11 (5.6 mg, 2 x10-3 mol) in 5 ml CDCl ml of the solution of 3 was titrated with 0.05 ml aliquots of the solution of 11. The mixture was kept at room temperature for 1/2 h, in order to ensure the establishment of H-bonding associations. -15-

16 Using the non-linear curve fitting procedure, [2] the K1 was calculated to be M -1 for 3:11, δ free = 8.05 ppm, δ dim = 9.55ppm and K1xK2 to be M -1 for 4:2(11), δ free = 8.05 ppm, δ dim = ppm. Job plot experiments Stock solutions (2 mm in CDCl 3 ) of 3 (or 4) and of 11 were prepared and mixed in NMR tubes with different host/guest ratios. In this way, relative concentrations, α, were varied continuously but their sum was kept constant. Job plots were obtained by plotting δα = (δ obs δ free ) α versus α, where δ free is the chemical shift of the NH ext in 3 (or 4). The stoichiometries of the 3:11 and 4:11 2 complexes were obtained from the value of the mole fraction α, which corresponds to a maximum of the curve: a 1 : 1 complexation was obtained for 3:11 with α max = 0.5. A 1 : 2 complexation was obtained for 4:11 with α max = Figure S5: Job plot experiment 3:11 Figure S6: Job plot experiment 4:11-16-

17 Figure S7: Changes of the P.L. intensity of 2 ( M) in CH 2 Cl 2 upon addition of 3 (0.0 to 3.0 equiv.); (λ exc = 375 nm) [1] K. A. Connors, Binding constants: the measurement of molecular complex stability, Wiley-Interscience, 1987, p. [2] a) L. Fielding, Tetrahedron 2000, 56, ; b) P. Thordarson, Chem. Soc. Rev. 2011, 40,

18 Crystal structure report Figure S8. X-ray crystallographic study for 3:10 with the atom labeling scheme. (C 84 H 83 Cl N 6 4 P 4 Ru, C 17 H 11 N 3 3 ); M = APEXII, Bruker-AXS diffractometer, Mo-Kα radiation (λ = Å), T = 150(2) K; monoclinic C 2/c (I.T.#15), a = (3), b = (13), c = (3) Å, β = (2), V = 23906(3) Å 3.Z = 8, d = g.cm -3, µ = mm -1. The structure was solved by direct methods using the SIR97 program [1], and then refined with full-matrix least-square methods based on F 2 (SHELXL-97) [2] with the aid of the WINGX [3] program. All non-hydrogen atoms were refined with anisotropic atomic displacement parameters. H atoms were finally included in their calculated positions. A final refinement on F 2 with unique intensities and 868 parameters converged at ωr(f 2 ) = (R(F) = ) for observed reflections with I > 2σ(I). [1] A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. Appl. Cryst. (1999) 32,

19 [2] Sheldrick G.M., Acta Cryst. A64 (2008), [3] L. J. Farrugia, J. Appl. Cryst., 2012, 45, [4] P. v.d. Sluis and A.L. Spek, Acta Cryst. (1990) A46, [5] A. L. Spek, J. Appl. Cryst. (2003), 36, 7-13 Table S2: Table 2. Selected Bond Lengths (Å) and Bond Angles (deg.) for 3:10. Bond Lengths [Å] Ru(1) - C(61) 2.009(5) N(217) H(217) 0.88 Ru(1) - P(4) (14) C(218) (222) 1.224(5) Ru(1) - P(3) (13) N(219) H(219) 0.88 Ru(1) - P(2) (13) C(220) (223) 1.214(5) Ru(1) - P(1) (14) C(216) (221) 1.210(5) Ru(1) - Cl(1) (11) C(71) - (72) 1.257(5) C(61) - C(62) 1.202(6) N(73) - H(73) 0.88 C(62) - C(63) 1.433(6) Angles [deg.] C(91) - (92) 1.204(5) N(93) - H(93) 0.88 N(100) H(100) 0.88 N(80) - H(80) 0.88 C(61)- Ru(1) - P(4) 81.26(15) P(4) - Ru(1) - P(1) (4) C(61)- Ru(1) - P(3) 85.95(12) P(3) - Ru(1) - P(1) 99.00(5) P(4) - Ru(1) - P(3) 82.44(5) P(2) - Ru(1) - P(1) 82.46(5) C(61)- Ru(1) - P(2) 89.32(12) C(61)- Ru(1) - Cl(1) (13) P(4) - Ru(1) - P(2) 95.93(5) P(4) - Ru(1) - Cl(1) (4) P(3) - Ru(1) - P(2) (4) P(3) - Ru(1) - Cl(1) 95.55(4) C(61)- Ru(1) - P(1) 96.64(15) P(2) - Ru(1) - Cl(1) 89.20(4) C(62)- C(61) - Ru(1) 174.6(5) P(1) - Ru(1) - Cl( (4) C(61)- C(62) - C(63) 177.7(6) Hydrogen bonds [Å and deg.] H(73)... (222) 2.1 N(73)- H(73)... (222) 2.974(5) H(80)... (221) 2.11 N(80)- H(80)... (221) 2.962(5) H(93)... (222) 2.12 N(93)- H(93)... (222) 2.978(5) H(100)...(223) 2.09 N(100)-H(100)... (223) 2.946(5) H(217)...N(79) 2.14 N(217)-H(217)... N(79) 2.920(5) H(219)...N(99) 2.06 N(219)-H(219)... N(99) 2.896(5) -19-

20 Table S3: Structural data Empirical formula C 101 H 94 Cl N 9 7 P 4 Ru Extendedformula C 84 H 83 Cl N 6 4 P 4 Ru, C 17 H 11 N 3 3 Formula weight Temperature 150(2) K Wavelength Å Crystal system, space group monoclinic, C 2/c Unit cell dimensions a = (3) Å, α = 90 b = (13) Å, β = (2) c = (3) Å, γ = 90 Volume 23906(3) Å 3 Z, Calculated density 8, (g.cm -3 ) Absorption coefficient mm -1 F(000) 7520 Crystal size 0.32 x 0.15 x 0.08 mm Crystal color yellow Theta range for data collection 2.92 to h_min, h_max -42, 41 k_min, k_max -22, 19 l_min, l_max -44, 56 Reflections collected / unique / [R(int) a = ] Reflections [I>2σ] Completeness to theta_max Absorption correction type multi-scan Max. and min. transmission 0.980, Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 27 / 868 b Goodness-of-fit Final R indices [I>2σ] R1 c = , wr2 d = R indices (all data) R1 c = , wr2 d = Largest diff. peak and hole and e -.Å -3 a R int = F o 2 b S = { [w(f o 2 - < F o 2 > / [F o 2 ] - F c 2 ) 2 ] / (n - p)} 1/2 c R1 = F o - F c / F o d wr2 = { [w(f o 2 - F c 2 ) 2 ] / [w(f o 2 ) 2 ]} 1/2 w = 1 / [σ(f o 2 ) + ap 2 + bp] where P = [2F c 2 + MAX(F o 2, 0)] /3-20-

21 Atom x y z occ. U(eq) Ru (13) (2) (8) (13) Cl (4) (7) (2) (3) P (4) (7) (3) (3) P (4) (7) (3) (3) P (4) (7) (3) (3) P (4) (7) (3) (3) C (17) (3) (11) (14) C (2) (4) (13) (10) H C (2) (4) (14) (10) H C (2) (4) (13) (10) H C (2) (4) (13) (10) H C (2) (4) (14) (10) H C (16) (3) (10) (12) C (17) (3) (12) (7) H C (17) (3) (12) (7) H C (18) (3) (13) (7) H C (17) (3) (12) (7) H C (17) (3) (12) (7) H C (2) (3) (14) (8) C (2) (3) (13) (8) H C (2) (3) (14) (8) H C (2) (3) (14) (8) H

22 C (2) (3) (13) (8) H C (2) (3) (13) (8) H C (18) (3) (14) (7) C (18) (3) (14) (7) H C (18) (3) (14) (7) H C (19) (3) (14) (7) H C (18) (3) (14) (7) H C (19) (3) (14) (7) H C (16) (3) (11) (13) H25A H25B C (17) (3) (11) (13) H26A H26B C (2) (4) (13) (8) C (19) (4) (13) (8) H C (19) (4) (13) (8) H C (2) (4) (14) (8) H C (2) (4) (13) (8) H C (2) (4) (13) (8) H C (16) (3) (11) (13) C (2) (4) (14) (9) H C (2) (4) (13) (9) H C (2) (4) (14) (9) -22-

23 H C (2) (4) (14) (9) H C (2) (4) (14) (9) H C (2) (3) (14) (8) C (2) (3) (15) (8) H C (2) (3) (14) (8) H C (2) (3) (15) (8) H C (2) (3) (15) (8) H C (2) (4) (14) (8) H C (17) (3) (12) (13) C (18) (3) (13) (7) H C (18) (3) (14) (7) H C (19) (3) (13) (7) H C (18) (3) (13) (7) H C (18) (3) (14) (7) H C (18) (3) (12) (15) H55A H55B C (18) (3) (13) (15) H56A H56B C (15) (3) (11) (12) C (16) (3) (11) (13) C (16) (3) (10) (12) C (16) (3) (10) (12) H

24 C (15) (2) (10) (11) C (15) (3) (10) (11) H C (15) (2) (10) (11) C (15) (2) (10) (11) H C (16) (3) (10) (11) (11) (19) (8) (9) N (12) (2) (9) (10) H C (15) (3) (11) (12) C (19) (4) (14) (19) H C (2) (4) (17) (2) H C (19) (4) (13) (17) H C (15) (3) (10) (12) N (11) (2) (8) (9) N (12) (2) (9) (10) H C (16) (3) (11) (12) (13) (2) (8) (10) C (16) (3) (11) (12) H83A H83B C (18) (3) (12) (14) C (3) (4) (19) (3) H85A H85B H85C C (2) (4) (13) (2) H86A H86B H86C C (2) (3) (15) (19) H87A H87B

25 H87C C (16) (3) (10) (12) (11) (2) (8) (10) N (12) (2) (8) (9) H C (14) (3) (10) (11) C (16) (3) (12) (13) H C (17) (3) (13) (15) H C (16) (3) (12) (14) H C (14) (3) (10) (11) N (11) (2) (8) (9) N (12) (2) (8) (10) H C (16) (3) (11) (14) (13) (2) (8) (12) C (15) (3) (11) (13) H10A H10B C (16) (4) (12) (15) C (17) (4) (14) (2) H10C H10D H10E C (18) (4) (13) (19) H10F H10G H10H C (2) (4) (17) (2) H10I H10J H10K C (2) (4) (16) (9) H C (2) (3) (16) (9) H

26 C (2) (4) (16) (9) H C (2) (4) (16) (9) H C (2) (3) (16) (9) H C (2) (4) (16) (9) C (16) (3) (13) (14) C (16) (3) (13) (13) C (16) (3) (12) (13) C (17) (3) (12) (14) H C (16) (3) (11) (13) H C (14) (3) (10) (11) C (18) (3) (12) (14) H C (18) (3) (13) (15) H N (12) (2) (8) (9) C (14) (3) (9) (10) N (11) (2) (8) (8) H C (15) (3) (10) (11) N (11) (2) (8) (8) H C (15) (3) (10) (10) (10) (18) (7) (8) (9) (17) (7) (8) (10) (17) (7) (8) Anisotropic displacement parameters (Å 2 ) The anisotropic displacement factor exponent takes the form: -26-

27 -2π 2 [ h 2 a* 2 U h k a* b* U 12 ]. Atom U11 U22 U33 U23 U13 U12 Ru (3) (2) (19) (15) (16) (18) Cl (8) (7) (5) (5) (5) (6) P (8) (7) (6) (5) (6) (6) P (8) (6) (6) (5) (6) (6) P (9) (7) (7) (5) (6) (6) P (9) (7) (7) (5) (6) (6) C (3) 0.065(4) 0.032(3) 0.009(2) 0.005(2) 0.004(3) C (18) 0.145(3) (14) (17) (12) 0.012(2) C (18) 0.145(3) (14) (17) (12) 0.012(2) C (18) 0.145(3) (14) (17) (12) 0.012(2) C (18) 0.145(3) (14) (17) (12) 0.012(2) C (18) 0.145(3) (14) (17) (12) 0.012(2) C (3) 0.045(3) 0.030(2) 0.001(2) 0.003(2) (2) C (17) (17) (13) (12) (12) (14) C (17) (17) (13) (12) (12) (14) C (17) (17) (13) (12) (12) (14) C (17) (17) (13) (12) (12) (14) C (17) (17) (13) (12) (12) (14) C (2) (12) (15) (11) (14) (13) C (2) (12) (15) (11) (14) (13) C (2) (12) (15) (11) (14) (13) C (2) (12) (15) (11) (14) (13) C (2) (12) (15) (11) (14) (13) C (2) (12) (15) (11) (14) (13) C (17) (15) (16) (11) (13) (12) C (17) (15) (16) (11) (13) (12) C (17) (15) (16) (11) (13) (12) C (17) (15) (16) (11) (13) (12) C (17) (15) (16) (11) (13) (12) C (17) (15) (16) (11) (13) (12) C (3) 0.035(3) 0.044(3) 0.012(2) 0.006(2) 0.001(2) -27-

28 C (4) 0.030(3) 0.037(3) 0.005(2) 0.001(2) (3) C (19) 0.093(2) (14) (13) (13) (16) C (19) 0.093(2) (14) (13) (13) (16) C (19) 0.093(2) (14) (13) (13) (16) C (19) 0.093(2) (14) (13) (13) (16) C (19) 0.093(2) (14) (13) (13) (16) C (19) 0.093(2) (14) (13) (13) (16) C (3) 0.045(3) 0.042(3) 0.003(2) 0.005(2) (3) C (2) 0.103(2) (16) (16) (14) (18) C (2) 0.103(2) (16) (16) (14) (18) C (2) 0.103(2) (16) (16) (14) (18) C (2) 0.103(2) (16) (16) (14) (18) C (2) 0.103(2) (16) (16) (14) (18) C (2) (17) (15) (13) (14) (14) C (2) (17) (15) (13) (14) (14) C (2) (17) (15) (13) (14) (14) C (2) (17) (15) (13) (14) (14) C (2) (17) (15) (13) (14) (14) C (2) (17) (15) (13) (14) (14) C (3) 0.033(3) 0.048(3) 0.005(2) (3) (2) C (17) (14) (16) (12) (13) (13) C (17) (14) (16) (12) (13) (13) C (17) (14) (16) (12) (13) (13) C (17) (14) (16) (12) (13) (13) C (17) (14) (16) (12) (13) (13) C (4) 0.037(3) 0.048(3) 0.005(2) (3) (3) C (4) 0.028(3) 0.057(3) 0.008(2) (3) (3) C (3) 0.032(3) 0.040(3) 0.001(2) (2) (2) C (3) 0.034(3) 0.032(2) 0.012(2) (2) (2) C (3) 0.033(3) 0.027(2) (19) 0.001(2) (2) C (3) 0.033(3) 0.037(2) 0.006(2) 0.000(2) 0.000(2) C (3) 0.026(2) 0.033(2) (19) (2) 0.005(2) C (3) 0.036(3) 0.027(2) (19) 0.011(2) 0.003(2) C (3) 0.023(2) 0.031(2) (18) 0.000(2) (2) C (3) 0.027(2) 0.034(2) (19) (2) (2) C (3) 0.043(3) 0.034(2) 0.005(2) 0.008(2) 0.005(2) (2) 0.050(2) 0.057(2) (17) (18) (18) N (2) 0.046(2) 0.042(2) (19) (18) (19) -28-

29 C (3) 0.051(3) 0.042(3) 0.009(2) 0.015(2) 0.015(3) C (4) 0.077(4) 0.076(4) 0.040(3) 0.030(3) 0.032(4) C (4) 0.097(5) 0.109(5) 0.038(4) 0.058(4) 0.042(4) C (4) 0.087(5) 0.060(4) 0.027(3) 0.034(3) 0.017(4) C (3) 0.054(3) 0.033(2) 0.004(2) 0.012(2) 0.011(2) N (2) 0.040(2) 0.036(2) (17) (17) (18) N (2) 0.046(2) 0.036(2) (18) (18) 0.000(2) C (3) 0.047(3) 0.031(2) 0.002(2) 0.011(2) (3) (3) 0.055(2) (19) (17) 0.031(2) 0.012(2) C (3) 0.037(3) 0.035(2) 0.001(2) 0.016(2) (2) C (4) 0.048(3) 0.053(3) 0.005(3) 0.032(3) (3) C (7) 0.059(5) 0.120(6) 0.036(4) 0.064(6) 0.016(5) C (6) 0.080(5) 0.057(4) (3) 0.035(4) (4) C (5) 0.055(4) 0.076(4) (3) 0.053(4) (4) C (3) 0.039(3) 0.031(2) 0.007(2) 0.002(2) (3) (2) 0.059(2) 0.048(2) (18) (17) (2) N (2) 0.031(2) 0.034(2) (16) (17) (18) C (3) 0.049(3) 0.032(2) (2) 0.001(2) (2) C (3) 0.041(3) 0.053(3) 0.001(2) 0.003(3) (3) C (3) 0.061(4) 0.065(4) (3) (3) (3) C (3) 0.056(4) 0.048(3) (3) (2) (3) C (3) 0.041(3) 0.036(2) 0.001(2) 0.000(2) 0.000(2) N (2) 0.037(2) (18) (16) (15) (17) N (2) 0.044(2) 0.033(2) (17) (17) (19) C (3) 0.070(4) 0.031(3) (3) (2) 0.003(3) (3) 0.091(3) 0.035(2) 0.001(2) (19) (2) C (3) 0.073(4) 0.030(2) 0.008(2) 0.001(2) (3) C (3) 0.093(5) 0.039(3) 0.017(3) 0.006(2) 0.016(3) C (3) 0.123(6) 0.057(4) 0.023(4) (3) 0.015(4) C (4) 0.120(6) 0.056(4) 0.010(4) 0.009(3) 0.028(4) C (5) 0.088(5) 0.085(5) 0.022(4) 0.012(4) 0.039(4) C (2) (16) (18) (14) (17) (16) C (2) (16) (18) (14) (17) (16) C (2) (16) (18) (14) (17) (16) C (2) (16) (18) (14) (17) (16) C (2) (16) (18) (14) (17) (16) C (2) (16) (18) (14) (17) (16) C (3) 0.053(4) 0.058(3) 0.002(3) 0.009(3) (3) -29-

30 C (3) 0.038(3) 0.060(3) 0.012(2) 0.009(3) 0.006(2) C (3) 0.040(3) 0.051(3) 0.009(2) 0.008(2) 0.000(2) C (4) 0.054(3) 0.040(3) (2) 0.005(3) 0.025(3) C (3) 0.045(3) 0.031(2) 0.003(2) 0.004(2) 0.015(3) C (3) 0.036(3) 0.028(2) (19) (2) 0.005(2) C (4) 0.041(3) 0.048(3) 0.011(2) 0.027(3) 0.017(3) C (4) 0.052(3) 0.050(3) 0.023(3) 0.022(3) 0.019(3) N (2) 0.030(2) (18) (15) (16) (18) C (3) 0.032(3) 0.027(2) (18) (19) 0.003(2) N (2) 0.036(2) (19) (16) (15) (17) C (3) 0.035(3) 0.025(2) (19) 0.008(2) 0.001(2) N (2) 0.034(2) (18) (16) (15) (17) C (3) 0.032(3) 0.029(2) (19) 0.002(2) 0.000(2) (2) (19) (18) (15) (15) (16) (19) (18) 0.053(2) (14) (15) (14) (19) (19) (19) (14) (15) (15) -30-