Self-assembly of Tetra- and Hexameric Terpyridine-based Macrocycles Using Cd(II), Zn(II) and Fe(II)

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1 Self-assembly of Tetra- and Hexameric Terpyridine-based Macrocycles Using Cd(II), Zn(II) and Fe(II) Lei Wang, Zhe Zhang,, Xin Jiang, Jennifer A. Irvin, # Changlin Liu, Ming Wang,*, and Xiaopeng Li*, Department of Chemistry, University of South Florida, Tampa 33620, United States. College of Chemistry, Central China Normal University, Wuhan , China. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin , China. # Department of Chemistry and Biochemistry, Texas State University, San Marcos, TX 78666, United States. S1

2 Table of Contents 1. Synthesis of L. S2 2. General procedure.....s3 3. Synthesis of the ligands and complexes......s4-s11 4. ESI mass spectra data...s12-s H NMR, 13 C NMR, 2D COSY NMR and MALDI-TOF MS...S20-S41 6. References. S42 1. Synthesis of Ligand L S2

3 2. General Procedures. Compound 1 was synthesized according to the reported methods. 1 Column chromatography was conducted using SiO2 (VWR, um, 60Å) and the separated products were visualized by UV light. 1 H NMR and 13 C NMR spectra data were recorded on a Bruker Avance 400-MHz,500-MHz NMR spectrometer and Varian inova 400-MHz spectrometer in CDCl3 and CD3CN with TMS standard. 19 F NMR spectra data for organic compounds were recorded on a Varian inova 400-MHz spectrometer in CDCl3 (trichloro-fluoro-methane was added as reference, 0 ppm). 19 F NMR spectra data for complexes were recorded on a Bruker Avance 500-MHz spectrometer in CD3CN (PF6 was viewed as reference). 2 MALDI-TOF mass spectra were recorded with a Bruker AutoFlexII mass spectrometer using DCTB as matrix. ESI-MS was conducted on Waters Synapt G2 mass spectrometer with traveling wave ion mobility. The concentration of complexes is 5 mg/ml for NMR measurement and 2 mg/ml for ESI-MS measurement. The IM-MS experiments were performed Waters Synapt G2 under the following conditions: ESI capillary voltage, 3kV; sample cone voltage, 30 V; extraction cone voltage, 3.5 V; source temperature 100 ºC; desolvation temperature, 100 ºC; cone gas flow, 10 L/h; desolvation gas flow, 700 L/h (N2); source gas control, 0 ml/min; trap gas control, 2 ml/min; Helium cell gas control, 100 ml/min; ion mobility (IM) cell gas control, 30 ml/min; sample flow rate, 5 μl/min; IM traveling wave height, 25 V; and IM traveling wave velocity, 1000 m/s. Cyclic voltammetry measurements were performed on a GAMRY Reference 600 potentiost with a standard three-electrode configuration using a platinum button working electrode, a platinum flag counter electrode and a silver wire pseudo-reference electrode. The S3

4 electrochemical properties of these two complexes in DMF were studied in a three-electrode electrochemical cell with Bu4NPF6 (0.001 M) as electrolyte. TEM: The sample was dissolved in a mixed solvent of DMF/THF (v/v: 1:4) at a concentration of 5.0 mg/ml. The nanostructures were formed after 4-7 days and measured by depositing the solution on copper grids (carbon coated 400 mesh Cu grids purchased from The TEM images were taken with a FEI Morgagni transmission electron microscope. Energy-minimized molecular models of the macrocycles were conducted with Materials Studio version 4.2, using the Anneal and Geometry Optimization tasks in the Forcite module (Accelrys Software, Inc.). All counterions and alkyl chain were omitted. Geometry optimization used a universal force field with atom-based summation and cubic spline truncation for both the electrostatic and Van der Waals parameters. 3. Synthesis of the ligand and complexes C D F E H G J I K B A Compound 2. A mixture of 5-bromo-3-fluoro-2-hydroxybenzaldehyde (4.0 g, 18.3 mmol), 1-bromooctane (4.2 g, 22.0 mmol), K2CO3 (5.1 g, 36.6 mmol) and DMF (100 ml) was heated at 100 C overnight. The mixture was cooled to room temperature. After DMF was removed under reduced pressure, the crude product was purified by a silica gel column chromatography. Compound 2 was obtained as a yellowish oil (5.4 g, 82.0 %). 1 H NMR (400 S4

5 MHz, CDCl3) δ (s, 1H, Ph-H A ), 7.71 (dd, J = 2.5, 1.5 Hz, 1H, Ph-H B ), 7.45 (dd, J = 10.9, 2.5 Hz, 1H, Ph-H C ), 4.24 (td, J = 6.6, 2.0 Hz, 2H, Alkyl-H D ), (m, 2H, Alkyl-H E ), (m, 2H, Alkyl-H F ), 1.30 (m, 8H, Alkyl-H G, Alkyl-H H, Alkyl-H I and Alkyl-H J ), (m, 3H, Alkyl-H K ). 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , 75.50, 31.74, 29.95, 29.23, 29.15, 25.74, 22.60, F NMR (376 MHz, CDCl3) δ EI-MS (): Calcd. for [C15H20BrFO2 ] + : Found: Compound 3. To a solution of NaOH powder (2.4 g, 60mmol) in EtOH (50 ml), compound 2 (3.3 g, 10 mmol) and 2-acetylpyridine (2.66 g, 22 mmol) was added. After stirring at room temperature for 24 h, aqueous NH3 H2O (28%, 40 ml) was added, the resulting mixture was refluxed for 20 h. After cooling to room temperature, the solid was collected by suction filtration with CHCl3, light purple solid was obtained, the crude product was purified by column chromatography on silica gel with dichloromethane: methanol (100:0.5) as eluent to afford the product as a white solid (3.75 g, 59.8%). 1 H NMR (400 MHz, CDCl3) δ (m, 6H, tpy-h 6, tpy-h 3 and tpy-h a3 ), 7.88 (td, J = 7.8, 1.5 Hz, 2H, tpy-h 4 ), 7.49 (d, J = 1.9 Hz, 1H, Ph-H A ), (m, 3H, Ph-H B, tpy-h 5 ), 3.91 (t, J = 6.4 Hz,, 2H, Alkyl-H C ), 1.54 (m, 2H, Alkyl-H D ), 1.14 (m, 4H, Alkyl-H E, Alkyl-H F ), 1.00 (m, 6H, Alkyl-H g, Alkyl-H H, Alkyl-H I ), 0.77 (t, J = 7.2 Hz, 3H, Alkyl-H J ). 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , , , , , 74.70, 31.68, 29.86, 29.19, 29.00, 25.73, 22.53, F NMR (376 MHz, CDCl3) δ ESI-TOF (): Calcd. for [C29H29BrFN3O + H] + : Found: S5

6 Compound 4. To a Schlenk flask containing compound 3 (2.13 g, 4 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), CuI (30.4 mg, 0.16 mmol) and ethynyltrimethylsilane (1.18 g, 12 mmol) was added. After the removal of air and back-filled with nitrogen, 20 ml of triethylamine and 40 ml of THF was added. The suspension was then stirred at 65 C for 12 hours. After evaporating the solvent under vacuum, the residue was purified by column chromatography on silica gel with dichloromethane: methanol (100:0.5) as fluent to get compound 4 as a yellow solid (2.10 g, 95.4%). 1 H NMR (400 MHz, CDCl3) δ (m, 6H, tpy-h 6, tpy-h 3 and tpy-h a3 ), 7.86 (td, J = 7.8, 1.6 Hz, 2H, tpy-h 4 ), 7.49 (s, 1H, Ph-H A ), 7.33 (dd, J = 6.9, 5.2 Hz, 2H, tpy-h 5 ), 7.26 (dd, J = 11.6, 1.9 Hz, 1H, Ph-H B ), 3.97 (t, J = 6.2 Hz, 2H, Alkyl-H C ), (m, 2H, Alkyl-H D ), 1.15 (m, 4H, Alkyl-H E, Alkyl-H F ), (m, 6H, Alkyl-H g, Alkyl-H H, Alkyl-H I ), 0.77 (t, J = 7.2 Hz, 3H, Alkyl-H J ), 0.26 (s, 9H, TMS-H). 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , , , , , , 94.98, 74.80, 74.76, 31.83, 30.04, 29.34, 29.15, 25.88, 22.67, 14.16, F NMR (376 MHz, CDCl3) δ ESI-TOF (): Calcd. for [C34H38FN3O2Si + H] + : Found: B D F E H G J I K C A a Compound 5. Potassium carbonate (1.58 g, mmol) was added to a solution of compound 4 (2.10 g, 3.8 mmol) in 50 ml methanol. The mixture was stirred at room S6

7 temperature for 3h. After that, 50 ml of water was added, and the suspension was extracted with CHCl3. The combined organic layer was washed with brine, dried over anhydrous Na2SO4, and then concentrated in vacuo, the crude prude was was purified by column chromatography on silica gel with dichloromethane: methanol (100:0.5) to get compound 5 as a white solid (1.72 g, 94.5%). 1 H NMR (400 MHz, CDCl3) δ 8.73 (d, J = 4.5 Hz, 2H, tpy-h 6 ), 8.69 (m, 4H, tpy-h 3 and tpy-h a3 ), 7.89 (td, J = 7.9, 1.6 Hz, 2H, tpy-h 4 ), 7.83 (dd, J = 7.7, 1.5 Hz, 1H, Ph-H A ), 7.52 (s, 1H, Ph-H B ), (m, 2H, tpy-h 5 ) (t, J = 6.4 Hz, 2H, Alkyl-H D ), 3.10 (s, 1H, Ph-H C ), 1.59 (m, 2H, Alkyl-H E ), (m, 2H, Alkyl-H F ), 1.04 (m, 8H, Alkyl-H G, Alkyl-H H, Alkyl-H I and Alkyl-H J ), 0.79 (t, J = 7.2 Hz, 3H, Alkyl-H K ). 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , 77.66, 74.71, 74.66, 31.70, 29.92, 29.21, 29.02, 25.75, 22.54, F NMR (376 MHz, CDCl3) δ ESI-TOF (): Calcd. for [C31H30FN3O + H] + : Found: K J H I F G D E C A B a Ligand L:Under nitrogen, a mixture of Pd(PPh3)4 (52 mg, 0.05 mmol), CuI (7.6 mg, 0.04 S7

mmol), 1,3,5-triiodobenzene (407 mg, 0.9 mmol) and compound 5 (1.5 g, 3.1 mmol) in 25 ml DMSO and 15 ml Et3N was stirred at 80 ºC for 48 h. 150 ml water was added and used DCM to extract 3 times.

8 mmol), 1,3,5-triiodobenzene (407 mg, 0.9 mmol) and compound 5 (1.5 g, 3.1 mmol) in 25 ml DMSO and 15 ml Et3N was stirred at 80 ºC for 48 h. 150 ml water was added and used DCM to extract 3 times. After that, the organic layer was washed three times with water. DCM was removed and the residue was purified by column chromatography on SiO2 with chloroform (add 1 % ethanol) as eluent to afford L in 72 % yield as a white solid. 1 H NMR (500 MHz, CDCl3) δ (m, 6H, tpy-h 6 ), (m, 12H, tpy-h 3 and tpy-h a3 ), 7.91 (td, J = 9.8, 2.3 Hz, 6H, tpy-h 4 ), 7.69 (s, 3H, Ph-H A ), 7.59 (dd, J = 2.5, 1.6 Hz, 3H, Ph-H B ), (m, 9H, tpy-h 5 and Ph-H C ), 4.03 (td, J = 8.0, 1.0 Hz, 6H, Alkyl-H D ), (m, 6H, Alkyl-H E ), (m, 6H, Alkyl-H F ), (m, 6H, Alkyl-H J ), (m, 18H, Alkyl-H G, Alkyl-H H and Alkyl-H I ), 0.80 (t, J = 9.0 Hz, 9H, Alkyl-H K ). 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , , , , , , , , , , , , 89.14, 89.11, 88.18, 74.76, 74.70, 31.71, 29.94, 29.23, 29.03, 25.77, 22.55, F NMR (376 MHz, CDCl3) δ MALDI-TOF MS (): Calcd. for [C99H90F3N9O3 + H] Found: K J H I F G D E K' J' H' F' D' I' G' E' 6' C' B' a3' 3' 4' 5' A' C A B a S8

9 Complex Cd 6 L 4 : To a solution of ligand L (7.2 mg, 4.8 μmol) in CHCl3 (1 ml), a solution of Cd(NO3)2 4H2O (2.2 mg, 7.2 μmol) in MeOH (3 ml) was added; then the mixture was stirred at 50 ºC for 8 h. After cooling to room temperature, 200 mg NH4PF6 was added and observed red precipitate, and used water to wash and obtained product (yield: 91 %). 1 H NMR (500 MHz, CD3CN) δ 8.99 (s, 2H, tpy-h a3 ), 8.94 (s, 4H, tpy-h a3 ), 8.76 (d, J = 8.1 Hz, 2H, tpy-h 3 ), 8.69 (d, J = 8.2 Hz, 4H, tpy-h 3 ), 8.30 (d, J = 6.9 Hz, 2H,, tpy-h 4 ), (m, 6H, tpy-h 4 and tpy-h 6 ), 8.10 (s, 4H, tpy-h 6 ), 7.93 (s, 2H, Ph-H A ), 7.91 (s, 2H, Ph-H A and Ph-H B ), 7.88 (s, 2H, Ph-H B ), 7.76 (d, J = 11.4 Hz, 1H, Ph-H C ), 7.70 (d, J = 12.0 Hz, 2H, Ph-H C ), (m, 2H, tpy-h 5 ), (m, 4H, tpy-h 5 ), 4.26 (m, 6H, Alkyl-H D and Alkyl-H D ), (m, 6H, Alkyl-H E and Alkyl-H E ), 1.30 (m, 6H, Alkyl-H F and Alkyl-H F ), 1.14 (m, 6H, Alkyl-H G and Alkyl-H G ), 0.91 (m, 18H, Alkyl-H H, Alkyl-H H Alkyl-H I, Alkyl-H I, Alkyl-H J and Alkyl-H J ), 0.66 (m, 9H, Alkyl-H K and Alkyl-H K ). 13 C NMR (125 MHz, CD3CN) δ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 88.91, 88.27, 75.19, 75.14, 31.46, 31.43, 29.99, 29.94, 29.16, 29.09, 29.04, 29.01, 26.11, 25.98, 22.26, 22.21, 13.28, F NMR (471 MHz, CD3CN) δ , ESI-MS (): [M-4PF6 ] 4+ (calcd : ), [M-5PF6 ] 5+ (calcd : ), [M-6PF6 ] 6+ (calcd : ), [M-7PF6 ] 7+ (calcd : ), [M-8PF6 ] 8+ (calcd : 912.3), [M-9PF6 ] 9+ (calcd : 794.7) and [M-10PF6 ] 10+ (calcd : 700.8). S9

10 K J H I F G D E K' J' H' F' D' I' G' E' 6' C' B' a3' 3' 4' 5' A' C A B a Complexes Zn 6 L 4 and Zn 9 L 6 : To a solution of ligand L (7.0 mg, 4.6 μmol) in CHCl3 (1 ml), a solution of Zn(NO3)2 6H2O (2.1 mg, 7.0 μmol) in MeOH (3 ml) was added; then the mixture was stirred at 50 ºC for 8 h. After cooling to room temperature, 200 mg NH4PF6 was added and observed yellow precipitate, and used water to wash and obtained product (yield: 83%). 19 F NMR (471 MHz, CD3CN) δ , ESI-MS (): [M-4PF6 ] 4+ (calcd : ), [M-5PF6 ] 5+ (calcd : ), [M-6PF6 ] 6+ (calcd : ), [M-7PF6 ] 7+ (calcd : ), [M-8PF6 ] 8+ (calcd : 876.9), [M-9PF6 ] 9+ (calcd : 763.4), [M-10PF6 ] 10+ (calcd : 672.5) and [M-11PF6 ] 11+ (calcd : 598.3) for Zn 6 L [M-8PF6 ] 8+ (calcd : ), [M-10PF6 ] 10+ (calcd : ) and [M-11PF6 ] 11+ (calcd : 969.8) for Zn 9 L 6. S10

K J H I F G D E K' J' H' F' D' I' G' E' 6' C' B' a3' 3' 4' 5' A' C A B a3 3 6 4 5 Complexes Fe 6 L 4 and Fe 9 L 6 : Ligand L (56 mg, 37.1 µmol) and FeSO4.7H2O (15.5 mg, 55.

After that the solution was cooled down and added into a 60 ml methanol solution with 2 g NH4PF6.

11 K J H I F G D E K' J' H' F' D' I' G' E' 6' C' B' a3' 3' 4' 5' A' C A B a Complexes Fe 6 L 4 and Fe 9 L 6 : Ligand L (56 mg, 37.1 µmol) and FeSO4.7H2O (15.5 mg, 55.7 µmol) were dissolved in 40 ml ethylene glycol. The solution was heated at 160 o C for 3 d under N2 protection. After that the solution was cooled down and added into a 60 ml methanol solution with 2 g NH4PF6. This solution was centrifuged and residue was flash column chromatographed (SiO2) eluting with MeCN/sat.KNO3(aq) (100:0-100:15). After removal of the volatile, the mixture was filtered and washed with water. The solid were dissolved in methanol (4 ml) and was dropped into a solution with NH4PF6 (240 mg in 8 ml methanol). Purple precipitate was washed with water and obtained product as a solid. Fe 6 L 4. (yield: 23%). 1 H NMR (500 MHz, CD3CN) δ 9.20 (s, 2H, tpy-h a3 ), 9.17 (s, 4H, tpy-h a3 ), 8.62 (d, J = 8.1 Hz, 2H, tpy-h 3 ), 8.51 (d, J = 8.0 Hz, 4H, tpy-h 3 ), 8.14 (s, 1H, Ph-H A ), 8.09 (s, 2H, Ph-H A ), (m, 3H, tpy-h 4 and Ph-H B ), 7.91 (d, J = 1.3 Hz, 2H, Ph-H B ), 7.73 (m, 7H, tpy-h 4, Ph-H C and Ph-H C ), 7.23 (d, J = 5.4 Hz, 2H, tpy-h 6 ), (m, 2H, tpy-h 5 ), 7.10 (d, J = 5.5 Hz, 4H, tpy-h 6 ), 6.99 (t, J = 6.6 Hz, 2H, tpy-h 5 ), 4.44 (t, J = 5.7 Hz, 2H, Alkyl-H D ), 4.33 (t, J = 5.6 Hz, 4H, Alkyl-H D ), (m, 2H, Alkyl-H E ), (m, 4H, Alkyl-H E ), 1.50 (m, 2H, Alkyl-H F ), 1.38 (m, 4H, Alkyl-H F ), S11

12 (m, 2H, Alkyl-H G ), 1.12 (m, 4H, Alkyl-H G ), 0.96 (m, 6H, Alkyl-H H, Alkyl-H I and Alkyl-H J ), 0.82 (m, 12H, Alkyl-H H, Alkyl-H I and Alkyl-H J ), 0.62 (t, J = 6.8 Hz, 3H, Alkyl-H K ), 0.53 (t, J = 6.8 Hz, 6H, Alkyl-H K ). 13 C NMR (125 MHz, DMSO) δ , , , , , , , , , , , , , , , , , , , , , , , , , , 89.51, 88.92, 75.88, 75.84, 31.91, 30.76, 30.68, 30.44, 29.87, 29.73, 29.58, 26.96, 26.75, 22.68, F NMR (471 MHz, CD3CN) δ , ESI-MS (): [M-5PF6 ] 5+ (calcd : ), [M-6PF6 ] 6+ (calcd : ), [M-7PF6 ] 7+ (calcd : ), [M-8PF6 ] 8+ (calcd : 869.8), [M-9PF6 ] 9+ (calcd : 757.1), [M-10PF6 ] 10+ (calcd : 666.8), [M-11PF6 ] 11+ (calcd : 593.1) and [M-12PF6 ] 12+ (calcd : 592.6). Fe 9 L 6. (yield: 50%). 1 H NMR (500 MHz, CD3CN) δ 9.25 (s, 2H, tpy-h a3 ), 9.16 (s, 4H, tpy-h a3 ), 8.66 (d, J = 8.0 Hz, 2H, tpy-h 3 ), 8.54 (d, J = 8.0 Hz, 4H, tpy-h 3 ), 8.16 (s, 1H, Ph-H A ), 8.14 (s, 2H, Ph-H A ), (m, 3H, tpy-h 4, Ph-H B ), 7.94 (d, J = 1.5 Hz, 2H, Ph-H B ), (m, 7H, tpy-h 4, Ph-H C and Ph-H C ), 7.27 (d, J = 5.3 Hz, 2H, tpy-h 6 ), (m, 2H, tpy-h 5 ), 7.14 (d, J = 5.7 Hz, 4H, tpy-h 6 ), (m, 4H, tpy-h 5 ), 4.43 (t, J = 5.4 Hz, 2H, Alkyl-H D ), 4.34 (t, J = 5.6 Hz, 4H, Alkyl-H D ), 1.84 (m, 2H, Alkyl-H E ), (m, 4H, Alkyl-H E ), 1.48 (m, 2H, Alkyl-H F ), 1.39 (m, 4H, Alkyl-H F ), 1.21 (m, 2H, Alkyl-H G ), 1.13 (m, 4H, Alkyl-H G ), (m, 18H, Alkyl-H H, Alkyl-H H, Alkyl-H I, Alkyl-H I, Alkyl-H J and Alkyl-H J ), 0.62 (t, J = 6.9 Hz, 3H, Alkyl-H K ), 0.57 (t, J = 6.9 Hz, 6H, Alkyl-H K ). 13 C NMR (125 MHz, CD3CN) δ , , , , , , , , , , , , , , , S12

13 130.12, , , , , , , , , , , 89.10, 88.34, 75.32, 75.25, 31.39, 31.34, 30.19, 30.12, 29.88, 29.30, 29.18, 29.12, 29.02, 26.37, 26.19, 22.11, F NMR (471 MHz, CD3CN) δ , ESI-MS (): [M-6PF6 ] 6+ (calcd : ), [M-7PF6 ] 7+ (calcd : ), [M-8PF6 ] 8+ (calcd : ), [M-9PF6 ] 9+ (calcd : ), [M-10PF6 ] 10+ (calcd : ), [M-11PF6 ] 11+ (calcd : 962.1), [M-12PF6 ] 12+ (calcd : 869.9), [M-13PF6 ] 13+ (calcd : 791.8), [M-14PF6 ] 14+ (calcd : 724.9), [M-15PF6 ] 15+ (calcd : 666.9), [M-16PF6 ] 16+ (calcd : 616.2) and [M-17PF6 ] 17+ (calcd : 571.4). Dimer Zn 2 L 2 : To a solution of ligand L (7.6 mg, 5.0 μmol) in CHCl3 (1 ml), a solution of Zn(NO3)2 6H2O (1.4 mg, 5.0 μmol) in MeOH (3 ml) was added; then the mixture was stirred at 50 ºC for 8 h. After cooling to room temperature, 100 mg NH4PF6 was added and yellow precipitate was observed. The precipitate was washed with water by centrifugation and dried under vacuum (yield: 90 %). ESI-MS (): [M-4PF6 ] 4+ (calcd : 788.1), [M-3PF6 ] 3+ (calcd : ), [M-2PF6 ] 2+ (calcd : ). 1 H NMR (500 MHz, CD3CN) shows small portion of supramolecular complexes inside which indicates stability of the favoured macrocycles. Dimer Cd 2 L 2 : To a solution of ligand L (7.6 mg, 5.0 μmol) in CHCl3 (1 ml), a solution of Cd(NO3)2 4H2O (1.5 mg, 5.0 μmol) in MeOH (3 ml) was added; then the mixture was stirred at 50 ºC for 8 h. After cooling to room temperature, 100 mg NH4PF6 was added and yellow precipitate was observed. The precipitate was washed with water by centrifugation and dried S13

14 under vacuum (yield: 90 %). ESI-MS (): [M-4PF6 ] 4+ (calcd : 811.6), [M-3PF6 ] 3+ (calcd : ), [M-2PF6 ] 2+ (calcd : ). 1 H NMR (500 MHz, CD3CN) shows small portion of supramolecular complexes inside which indicates stability of the favoured macrocycles. Dimer Fe 2 L 2 : Ligand L (56 mg, 37.1 µmol) and FeSO4.7H2O (10.3 mg, 37.1 µmol) were dissolved in 20 ml ethylene glycol. The solution was heated at 160 o C for overnight under N2 protection. After that the solution was cooled down and added into a 60 ml methanol solution with 1 g NH4PF6. This solution was centrifuged and residue was flash column chromatographed (SiO2) eluting with MeCN/sat.KNO3(aq) (100:0-100:6). After removal of the volatile, the mixture was filtered and washed with water. The solid were dissolved in chloroform (2 ml) and was dropped into a solution with NH4PF6 (100 mg in 8 ml methanol). Purple precipitate was washed with water and obtained product as a purple solid (yield 57 %). 1 H NMR (500 MHz, CD3CN) δ 9.18 (s, 8H, tpy-h a3 ), 8.80 (m, 8H, tpy-h 6, tpy-h 3 ), 8.75 (s, 4H, tpy-h a3 ), 8.54 (d, J = 7.9 Hz, 8H, tpy-h 3 ), 8.09 (m, 8H, tpy-h 4, Ph-H A ), 7.90 (m, 6H, Ph-H A and Ph-H B ), 7.84 (m, 8H, tpy-h 4 ), 7.76 (d, J = 11.8 Hz, 4H, Ph-H C ), 7.69 (s, 2H, S14

15 Ph-H B ), 7.59 (d, J = 11.6 Hz, 2H, Ph-H C ), 7.54 (m, 4H, tpy-h 5 ), 7.14 (m, 8H, tpy-h 6 ), 7.05 (m, 8H, tpy-h 5 ), 4.36 (t, J = 5.6 Hz, 8H, Alkyl-H D ), 4.10 (t, J = 5.4 Hz, 4H, Alkyl-H D ), 1.79 (m, 8H, Alkyl-H E ), 1.60 (m, 4H, Alkyl-H E ), 1.42 (m, 8H, Alkyl-H F ), 1.15 (m, 16H, Alkyl-H G and Alkyl-H H ), (m, 44H, Alkyl-H I and Alkyl-H J, Alkyl-H F-K ), 0.59 ((t, J = 6.9 Hz, 12H, Alkyl-H K ). 19 F NMR (471 MHz, CD3CN) δ , ESI-MS (): [M-4PF6 ] 4+ (calcd : 783.3), [M-3PF6 ] 3+ (calcd : ), [M-2PF6 ] 2+ (calcd : ). S15

16 4. ESI mass spectra data (PF 6 as counterion) (A) [Fe 6 L 4 ] = [Fe 9 L 6 ] = (B) Drift Time (ms) Figure S1. (A) ESI-MS and (B) 2D ESI-IM-MS spectra ( vs. drift time) of mixture Fe 6 L 4 and Fe 9 L 6 before column chromatography. The charge states of intact assemblies are marked. S16

17 Cd 6 L Figure S2. Measured (bottom) and calculated (top) isotope patterns for the different charge states (4+ to 9+) observed from Cd 6 L 4 (PF6 as counterion). S17

18 Zn 6 L S18

19 Figure S3. Measured (bottom) and calculated (top) isotope patterns for the different charge states (5+ to 11+) observed from Zn 6 L 4 (PF6 as counterion). Zn 9 L Figure S4. Measured (bottom) and calculated (top) isotope patterns for the different charge S19

20 states (8+ to 11+) observed from Zn 9 L 6 (PF6 as counterion). Fe 6 L S20

21 Figure S5. Measured (bottom) and calculated (top) isotope patterns for the different charge states (5+ to 12+) observed from Fe 6 L 4 (PF6 as counterion). Fe 9 L S21

22 S22

23 Figure S6. Measured (bottom) and calculated (top) isotope patterns for the different charge states (6+ to 17+) observed from Fe 9 L 6 (PF6 as counterion) Theoretical Experimental Figure S7. ESI-MS and isotope pattern of the dimer obtained by the self-assembly of ligand L with Zn 2+ at molar ratio 1:1. S23

24 Theoretical Experimental Figure S8. ESI-MS and isotope pattern of the dimer obtained by the self-assembly of ligand L with Fe 2+ at molar ratio 1:1. S24

25 Figure S9. ESI-MS spectra of Cd 6 L 4 under different concentration (0.5 mg/ml-8.0 mg/ml, top to bottom). S25

26 8+ 6+ [Zn 6 L 4 ] = [Zn 9 L 6 ] = Figure S10. ESI-MS spectra of mixture Zn 6 L 4 and Zn 9 L 6 under different concentration (0.5 mg/ml-8.0 mg/ml, top to bottom). S26

27 5. 1 H NMR, 13 C NMR, 19 F NMR and 2D COSY NMR Figure S11. 1 H NMR (500 MHz) spectrum of ligand L. Figure S C NMR (500 MHz) spectrum of ligand L. S27

28 Figure S13. 2D COSY NMR (500 MHz) spectrum of ligand L. S28

29 6 a3 3 A 4 B C 5 Figure S14. 2D COSY NMR (500 MHz) spectrum of ligand L (aromatic region). S29

30 K D E F J G H I Figure S15. 2D COSY NMR (500 MHz) spectrum of ligand L (aliphatic region). S30

31 Figure S F NMR (376 MHz) spectrum of ligand L Figure S17. MALDI-TOF mass spectrum of ligand L. S31

32 Figure S18. 1 H NMR (500 MHz) spectrum of complex Cd 6 L 4. S32

33 Figure S C NMR (500 MHz) spectrum of complex Cd 6 L 4. Figure S F NMR (471 MHz) spectrum of complex Cd 6 L 4. S33

34 Figure S21. 2D COSY NMR (500 MHz) spectrum of complex Cd 6 L 4. S34

3' 3 C' B' a3' 3' 4' 6' 5' 4' A' 4 C B A 6 6' a3 3 6 4 5 5' 5 Figure

35 3' 3 C' B' a3' 3' 4' 6' 5' 4' A' 4 C B A 6 6' a ' 5 Figure S22. 2D COSY NMR (500 MHz) spectrum of Cd 6 L 4 (aromatic region). S35

36 K J H I F G D E K' J' H' F' D' I' G' E' C' B' a3' 3' 4' 6' 5' A' C A B a H I J H' I' J' K K' D D' E E' F G F' G' Figure S23. 2D COSY NMR (500 MHz) spectrum of Cd 6 L 4 (aliphatic region). S36

37 Figure S24. 1 H NMR (500 MHz) spectrum of complex Zn 6 L 4 and Zn 9 L Figure S F NMR (471 MHz) spectrum of complex Zn 6 L 4 and Zn 9 L 6. S37

38 Figure S26. 2 D COSY NMR (500 MHz) spectrum of complex Zn 6 L 4 and Zn 9 L 6. S38

39 F C' O B' a3' N N 3' Zn N 4' 6' 5' A' F C A F O a3 B 3 O N N Zn N N N Zn N 6' 6' 3' ' 3 4' 6 4 5' 5 4' 5 5' Figure S27. 2 D COSY NMR (500 MHz) spectrum of complex Zn 6 L 4 and Zn 9 L 6 (aromatic region). S39

40 Figure S28. 1 H NMR (500 MHz) spectrum of complex Fe 6 L 4. Figure S C NMR (500 MHz) spectrum of complex Fe 6 L 4. S40

41 Figure S F NMR (471 MHz) spectrum of complex Fe 6 L 4. Figure S31. 2D COSY NMR (500 MHz) spectrum of Fe 6 L 4. S41

C' B' a3' 3' 4' 6' 5' A' C A B a3 3 4 5 6 a3' a3 3' 3 4' 4 6 6' 5' 5

42 C' B' a3' 3' 4' 6' 5' A' C A B a a3' a3 3' 3 4' 4 6 6' 5' 5 Figure S32. 2D COSY NMR (500 MHz) spectrum of Fe 6 L 4 (aromatic region). S42

43 K J H I F G D E K' J' H' F' D' I' G' E' D D' E E F' F G' G H I J H' I' J' K' K Figure S33. 2D COSY NMR (500 MHz) spectrum of Fe 6 L 4 (aliphatic region). S43

44 Figure S34. 1 H NMR (500 MHz) spectrum of complex Fe 9 L 6. Figure S C NMR (500 MHz) spectrum of complex Fe 9 L 6. S44

45 Figure S F NMR (471 MHz) spectrum of complex Fe 9 L 6. Figure S37. 2D COSY NMR (500 MHz) spectrum of complex Fe 9 L 6. S45

C' B' a3' 3' 4' 6' 5' A' C A B a3 3 4 5 6 a3 a3' 3' 3 4' 6 4 6' 5' 5

46 C' B' a3' 3' 4' 6' 5' A' C A B a a3 a3' 3' 3 4' 6 4 6' 5' 5 Figure S38. 2D COSY NMR (500 MHz) spectrum of Fe 9 L 6 (aromatic region). S46

47 K J H I F G D E K' J' H' F' D' I' G' E' D D' E'E H I J H' I' J' K' K F' F G' G Figure S39. 2D COSY NMR (500 MHz) spectrum of Fe 9 L 6 (aliphatic region). S47

48 Figure S40. 1 H NMR (500 MHz) spectrum of dimer Cd 2 L 2. Figure S41. 2D COSY NMR (500 MHz) spectrum of Cd 2 L 2. S48

49 a3 3 3 a3 3 6 a3 a3 3 b bc c a c 6 5 a a 4 4 b 4 b 5 a c Figure S42. 2D COSY NMR (500 MHz) spectrum of Cd 2 L 2 (aromatic region). S49

50 Figure S43. 1 H NMR (500 MHz) spectrum of dimer Zn 2 L 2. Figure S44. 2D COSY NMR (500 MHz) spectrum of Zn 2 L 2. S50

51 b c 6 a3 3 a 4 b 4 5 a3 6 a3 3 4 c b 3 3 a 6 5 a 4 b a3 a c c Figure S45. 2D COSY NMR (500 MHz) spectrum of Zn 2 L 2 (aromatic region). S51

52 Figure S46. 1 H NMR (500 MHz) spectrum of dimer Fe 2 L 2. Figure S F NMR (471 MHz) spectrum of dimer Fe 2 L 2. S52

53 Figure S48. 2D COSY NMR (500 MHz) spectrum of dimer Fe 2 L 2. S53

54 a3 6 a a 3 a b 4 5 c b c 5 Figure S49. 2D COSY NMR (500 MHz) spectrum of dimer Fe 2 L 2 (aromatic region). S54

55 6. References (1) Micklatcher, M. L.; Cushman, M. An Improved Method for the Synthesis of 3-Fluorosalicylic Acid with Application to the Synthesis of 3-(Trifluoromethyl) Salicylic Acid. Synthesis. 1999, 11, (2) Porras, J. A.; Mills, I. N.; Transue, W. J.; Bernhard, S. Highly Fluorinated Ir (III) 2, 2 : 6, 2 -Terpyridine Phenylpyridine X Complexes via Selective C F Activation: Robust Photocatalysts for Solar Fuel Generation and Photoredox Catalysis. J. Am. Chem. Soc. 2016, 138, S55

Directed flexibility: Self-assembly of a supramolecular tetrahedron

Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Electronic Supplemental Information Directed flexibility: Self-assembly of a supramolecular tetrahedron