Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008

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1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008

2 Metal-directed dynamic formation of tertiary structure in foldamer assemblies: Orienting helices at an angle Nicolas Delsuc, [a] Marie Hutin, [c] Victoria E. Campbell, [b] Brice Kauffmann, [a] Jonathan R. Nitschke,* [b] and Ivan Huc* [a] [a] Dr. I. Huc, Dr. N. Delsuc, Dr. B. Kauffman Institut Européen de Chimie et Biologie Université de Bordeaux CNRS UMR5248 and UMS rue Robert Escarpit, Pessac, France Fax: (+33) i.huc@iecb.u-bordeaux.fr [b] Dr. J. R. Nitschke, V. E. Campbell Department of Chemistry University of Cambridge Lensfield Road, Cambridge CB2 1EW, UK Fax: (+44) jrn34@cam.ac.uk [b] Dr. M. Hutin Département de chimie organique Université de Genève - Sciences II 30 quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland

3 Experimental section: Synthesis of 1. To a solution of tetramer 4 (150 mg, 0.15 mmol, 1 equiv.) in a mixture THF/MeOH (vol/vol 3.3:1.7 ml) was added ethylene diamine (195 µl, 3.0 mmol, 20 equiv.). The reaction mixture was stirred at room temperature for 3 hours. More ethylene diamine was added (195 µl, 3.0 mmol, 20 equiv.) ibuo and the reaction was stirred at 40 C for 16 hours, ethylene diamine (1.6 ml, 23.4 mmol, 160 equiv.) was again added and the reaction was stirred at 40 C for 2 days. The solvents were removed then the crude product was diluted in DCM (40mL) and washed with a solution of HCl 1N (20mL),then with water (20mL) and then with a saturated solution of NaHCO 3. The organic phase was dried with Na 2 SO 4, filtered, and evaporated. The product was purified by silica gel chromatography using DCM/Et 3 N/MeOH 94:5:1 vol/vol/vol to provide 136 mg (88 % yield) of 1. 1 H RMN (300MHz, CDCl 3 ) : δ = (1H, s), (1H, s), (1H, s), 9.08 (1H, dd, J=7.5Hz, J=1.0Hz), 8.58 (1H, dd, J=8.4Hz, J=1.2Hz), 8,34 (1H, dd, J=7.8Hz, J=1.2Hz), 8.17 (1H, dd J=7.5Hz, J=1.0Hz), 8.05 (1H, bs), 8.02 (1H, bs), 7.95 (1H, d, J=8.4Hz, J=1.2Hz), 7.83 (1H, s), 7.80 (1H, t, J=7.8Hz), ,54 (2H, m), 7.52 (1H, s), 7.40 (1H, t, J=8.1Hz), 7.28 (1H, t, J=8.1Hz), 6.90 (1H, s), 6.68 (1H, s), 4.28 (2H, bs), 4.23 (2H, d, J=6.6Hz), 3.91 (2H, d, J=6.6Hz), 3.88 (2H, d, J=6.6Hz), 3.62 (2H, m), (4H, m), (2H, m), (24H, m). 13 C RMN (75MHz, CDCl 3 ) : δ = 163.8; 163.7; 162.7; 162.5; 162.1; 160.8; 160.1; 153.1; 150.1; 148.6; 147.5; 144.5; 138.6; 138.4; 137.7; 137.6; 134.3; 133.0; 132.8; 127.6; 127.5; 126.3; 126.2; 125.5; 123.9; 123.4; 121.9; 121.6; 121.2; 117.3; 116.5; 116.4; 116.1; 116.0; 115.9; 99.8; 98.2; 97.8; 97.2; 75.4; 75.1; 74.8; 74.6; 38.8; 37.4; 27.8; 27.7; 27.6; 18.9; MS (maldi): m/z = [M+H] +, [M+Na] +. Synthesis of 2. Into an NMR tube with a Teflon screw-cap were added 1 ( g, 9.91 mmol) and Cu(NCMe) 4 BF 4 ( g, 4.77 mmol) and deuterated acetonitrile (0.2 ml) under argon. To this mixture a solution of 6-methyl-2-formylpyridine was added in deuterated dichloromethane (2 equiv, 0.05 ml of M solution), and 0.1 ml of pure deuterated dichloromethane. After one night at room temperature the solvents were removed under vacuum, and the residue was dissolved in pure deuterated solvent (dichloromethane, acetonitrile, methanol, benzene and DMSO) in a glove box with anaerobic atmosphere for NMR analyses. 1 H NMR: see Figure S1 below. ESI-MS: [1 terminal nitroquinoloyl ring] +, [2 ligand] +, [2] +. O N NO 2 ibuo NH N OMe O 3 4 ibuo N NO 2 1 O N H 4 NH 2 S2

4 Current Data Parameters NAME g5_mh-4-117c EXPNO 253 PROCNO 1 F2 - Acquisition Parameters Date_ Time INSTRUM drx500 PROBHD 5 mm QNP 1H/13 PULPROG zg30 TD SOLVENT CD3CN NS 32 DS 2 SWH Hz FIDRES Hz AQ sec RG 256 DW usec DE 7.00 usec TE K D sec MCREST sec MCWRK sec ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 - Processing parameters SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm Figure S1. 1 H NMR spectrum of 2 in dichloromethane-d 2 at 253 K S2. ESI-MS spectrum of 2 in methanol. Figure S3

5 Preparation of the mixture of 3 and 4. To an NMR tube fitted with a Teflon screw cap 2-formylpyridine ( g, mmol), 1 ( g, mmol), Fe(II)(CH 3 CN) 6 (BF 4 ) 2 ( g, mmol) and deuterated acetonitrile (0.5 ml) were added. The solution was purged of dioxygen with three evacuation/argon purge cycles. The purple solution was heated overnight at 50 o C. 1 H NMR: see Figure S3 below. ESI-MS: m/z = [1] +, [3] +, [4] 2+. Standard 1H DRX Current Data Parameters NAME VEC4066 EXPNO 2 PROCNO 1 F2 - Acquisition Parameters Date_ Time 9.36 INSTRUM drx400 PROBHD 5 mm Dual 13C/ PULPROG zg30 TD SOLVENT CD3CN NS 521 DS 2 SWH Hz FIDRES Hz AQ sec RG DW usec DE usec TE K D sec TD0 1 ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 - Processing parameters SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm Figure S3. 1 H NMR spectrum of the mixture of products formed upon mixture of 1, 2-formylpyridine and Fe(NCMe) 6 (BF 4 ) 2 in a 2:2:1 ratio in acetonitriled 3. S4

6 +TOF MS: to min from Victoria_ wiff a= e-004, t0= e [1] Max counts [3] [4] m/z, amu Figure S4. ESI-MS spectrum of the mixture of products formed upon mixture of 1, 2-formylpyridine and Fe(NCMe) 6 (BF 4 ) 2 in a 2:2:1 ratio in acetonitriled 3. Crystallographic studies Data for the structures of 2a and 2c were collected using a Rigaku Rapid diffractometer equipped with an MM007 microfocus rotating anode generator with monochromatized Cu-K α radiation ( Å), varimax optics and a RAPID image plate for two of the structures. The data collected on the crystal of compound 3 were measured using synchrotron radiation at ESRF in Grenoble (ID29 beamline). This beamline is tunable and we used a wavelength of 0.8 Å. The detector is an ADSC Q315R with an active area of 315 x 315 mm 2. The unit cell refinement and data reduction were performed using the CrystalClear and xprep software packages. The positions of non-h atoms were determined by the program SHELXD [1] and the position of H atoms were deduced from coordinates of the non-h atoms and confirmed by Fourier Synthesis. H atoms were included for structure factor calculations but not refined. The crystal structure of 2c belongs to the triclinic space group P-1 with unit cell dimensions: a = (4) Å, b = (5) Å, c = (6) Å, α = (3), β = 90.73(3), γ = (4), V = 14826(5) Å 3, and Z = 4 for two independent molecules in the asymmetric unit (FW is , ρ = Mg.m -3 ). Reflections were collected from 6.53 θ for a total of , of which were unique (R int = ) having I > 2σ(I); the number of parameters is Final R factors were R 1 = (I > 2σ(I)), S5

7 wr 2 = (all data), GOF = from SHELX, maximal residual electron density is e.å -3. CCDC # The crystal structure of 2a also belongs to the triclinic space group P-1 with unit cell dimensions: a = (2) Å, b = (2) Å, c = (2) Å, α = (6), β = (7), γ = (7), V = (13) Å 3, and Z = 2 (FW is , ρ = Mg.m -3 ). Reflections were collected from 6.54 θ for a total of of which were unique (R int = ) having I > 2σ(I); the number of parameters is Final R factors were R 1 = (I > 2σ(I)), wr 2 = (all data), GOF = from SHELX, maximal residual electron density is e.å -3. CCDC # The crystal of 3 belongs to the triclinic space group P-1 with unit cell dimensions: a = (3) Å, b = (6) Å, c = (7) Å, α = 89.87(3), β = 89.82(3), γ = 89.55(3), V = 13906(5) Å 3, and Z = 4 for two independent molecules in the asymmetric unit (FW is , ρ = Mg.m -3 ). Reflections were collected using a phi scan and 360 rotation to a maximum resolution of 1.2 Å for a total of of which were unique (R int = ) having I > 2σ(I); the number of parameters is Final R factors were R 1 = (I > 2σ(I)), wr 2 = (all data), GOF = from SHELX, maximal residual electron density is e.å -3. It was noticed during data collection a dramatic effect of the high intensity beam on the diffraction of the crystal. This radiation damage could explain the poor statistics during refinement of the structure. CCDC # [1] G. M. Sheldrick, Acta Cryst. 2008, A64, S6