Supporting Information

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1 Supporting Information Interlocked Supramolecular Polymers Created by Combination of Halogen- and Hydrogen- Bonding Interactions Through Anion-Template Self-Assembly Fabiola Zapata, Lidia González, Antonio Caballero,* Adolfo Bastida, Delia Bautista, and Pedro Molina.* Departamento de Química Orgánica, Universidad de Murcia, Campus de Espinardo, 30100, Murcia, Spain Departamento de Química Física, Universidad de Murcia, Campus de Espinardo, 30100, Murcia, Spain Servicio de Apoyo a la Investigación, Universidad de Murcia, Campus de Espinardo, E-30071, Murcia, Spain Table of Contents Experimental Procedures S2 PART I: Synthesis S3 PART II: 1 H NMR Experiments S6 PART III: Cooperative model analyses. S9 PART IV: SEM images. S11 PART V: X-ray. S13 PART VI: Fluorescence Studies. S15 Part VI: 1 H-NMR titration experiment of the proto-triazolium analogue S16 References S18 S1

2 Experimental Procedures THF and dichloromethane were dried distilling from sodium or calcium hydride respectively. All melting points were determined by means of a Kofler hot-plate melting-point apparatus and are uncorrected. Solution 1 H-, and 13 C-NMR spectra were recorded with Bruker 200, 300, 400, or 600 MHz spectrometers. The following abbreviations have been used to state the multiplicity of the signals: s (singlet), d (doublet), t (triplet) and m (multiplet). Chemical shifts (δ) in the 1 H and 13 C NMR spectra are referenced to tetramethylsilane (TMS). Diffusion NMR experiments (DOSY) were recorded with a Bruker 600 spectrometer (1H) using the LED-BPP sequence with a diffusion period ( ) of 150 ms, field gradient pulses (δ) of 4 ms applied as half-sine profile bipolar pairs and an LED period of 5 ms. Field gradients were varied from 2-90% of maximum (53 G/cm) in 16 steps and data were analysed using Bruker TOPSPIN 2.1 software. Sample temperature was regulated at 293K. UV vis and fluorescence spectra were carried out in the solvents and concentrations stated in the text and in the corresponding figure captions, using a dissolution cell with 10 mm path length, and they were recorded with the spectra background corrected before and after sequential additions of different aliquots of anions Mass spectra were recorded with a Fisons AUTOSPEC 500 VG spectrometer and FAB+ mass spectra were carried out with 3-nitrobenzylalcohol as a matrix. Microanalyses were performed with a Carlo Erba 1108 instrument. Dynamic Light Scattering analyses were performed using a Malvern Zetasizer Nano ZS (Malvern Instruments Ltd, UK) at 25ºC and a 173 angle relative to the source. The hydrodynamic diameter distributions were obtained by volume using the software package of the apparatus. Each curve represents the average of 3 measurements (16 runs each). Prior to analysis, all solutions were filtered. Scaning electron microscopy (SEM) was perfermed using a JSM-6100 scanning microscope instrument and the images were obtained with the INCA software (Oxford Instrument). The samples were prepared on cover glass, which was cleaned using nitric acid prior to use. The cover glass was then dropped into a polymer solution in CH 3 CN/MeOH 9:1. The supramolecular polymer in solid state on the cover glass was obtained by the vapour diffusion of diethyl ether into a solution of the polymer. Then the cover glass was dried for 16h at 25ºC and the gold film was deposited by a SEM coating system Bio Rad Polaron Division prior to perform the analyses. X-Ray Structure Determinations. Intensities were registered at low temperature on a Bruker D8QUEST diffractometer using monochromated Mo Kα radiation (λ = Å). Absorption corrections were based on multi-scans (program SADABS). Structures were refined anisotropically using SHELXL [1] Hydrogen atoms were included using rigid methyl groups or a riding model. Special features and exceptions: The iodine atoms are disordered over two positions, I1 (64:38%) and I2 (52:48%). One NO 2 ligand is disordered over two positions, 51:49%. The sulphate anion is also disordered over two positions, 69:32%. S2

3 PART I: Synthesis Scheme S1. Synthesis of the monomer BF 4 -. S3

4 Synthesis of the bis-iodotriazole 4 Copper iodide (0.052 g 0.27 mmol) and TBTA (0.146 g, 0.27 mmol) were stirred in dry THF (10 ml) for 20 min. The catalyst solution was added to a solution (30 ml THF) of iodoalkyne 3 (0.450 g, 1.64 mmol) and azide 2 (0.205 g, 0.69 mmol) and the reaction left to stir in the dark for 48 h at r.t. before being quenched with 10 % ammonium hydroxide solution (30 ml). The mixture is allowed to stir for 15 minutes, appearing a pale yellow solid which is filled in vacuo. The solid is washed with more ammonium hydroxide solution (30 ml) and water (120 ml) and finally with methanol (50 ml). Yield=(0.378 g, 65 %); m.p. 226ºC (decomposes); 1 H NMR- δ (DMSO-d 6, 300MHz): 8.34 (d, 4H, J=8.9Hz), 8.17 (d, 4H, J=8.9Hz), 7.67 (d, 2H, J=8.9Hz), 7.22 (d, 2H, J=2.2Hz), 6.91 (dd, 2H, J=2.2Hz, J=8.9Hz), 4.91 (t, 4H, J=4.9Hz), 4.56 (t, 4H, J=4.9Hz); 13 C NMR- δ (DMSO-d 6, 150MHz): 156.3, 146.9, 146.6, 136.9, 135.5, 129.3, 127.7, 124.2, 124.1, 116.0, 106.6, 84.7, 66.0, 49.9; MS (ESI): m/z calc. for C 30 H 22 I 2 N 8 O 6 [M+1] , found H-NMR 13 C-NMR S4

5 Synthesis of the monomer BF 4 -. A solution of bis-iodotriazole 4 (0.200 g, 0.24 mmol) in dry dichloromethane (15 ml) was treated with trimethyloxonium tetrafluoroborate (0.087 g, 0.59 mmol) and the reaction mixture left to stir under N 2 for 72 h at r.t. and then all volatile components were removed in vacuo to give a yellow oil, which was purified by silica gel column chromatography (eluent CH 2 Cl 2 /CH 3 OH 8:2) to give an yellow solid. Yield=(0.085 g, 34 %); m.p. 198 ºC (descomposes); 1 H NMR- δ (CD 3 CN/CD 3 OD 9:1, 600MHz): 8.46 (d, 4H, J=8.9Hz), 7.79 (d, 4H, J=8.9Hz), 7.75 (d, 2H, J=9Hz), 7.23 (d, 2H, J= 2.5Hz), 7.04 (dd, 2H, J=2.5Hz, J=9Hz), 5.13 ( t, 4H, J=4.8Hz), 4.64 (t, 4H, J=4.8Hz), 4.15 (s, 6H); 13 C NMR- δ (CD 3 CN, 100MHz): 158.1, 151.7, 146.9, 137.3, 133.6, 131.1, 130.4, 126.6, 126.3, 118.0, 108.3, 93.2, 67.0, 55.9, 41.1; MS (ESI): m/z calc. for C 32 H 28 B 2 F 8 I 2 N 8 O 6 [M +2 /2] , found H-NMR 13 C-NMR S5

6 PART II: 1 H NMR Experiments Figure S1. 1 H NMR spectral changes observed in BF 4 - in CD 3 CN/CD 3 OD (9/1, v/v) during the addition of up to 40 equiv of H 2 PO 4 - anions. Figure S2. 1 H NMR spectral changes observed in BF 4 - in CD 3 CN/CD 3 OD (9/1, v/v) during the addition of up to 20 equiv of SO 4 2- anions. S6

7 Figure S3. 1 H NMR spectral changes observed in BF 4 - in CD 3 CN/CD 3 OD (9/1, v/v) during the addition of up to 13 equiv of HP 2 O 7 3- anions. Figure S4. Job plot experiment with a maximum at 0.5 indicating 1:1 stoichiometry for receptor BF 4 - and SO 4 2- in CD 3 CN/CD 3 OD (9/1, v/v). Figure S5. Job plot experiment with a maximum at 0.5 indicating 1:1 stoichiometry for receptor BF 4 - and HP 2 O 7 3- in CD 3 CN/CD 3 OD (9/1, v/v). S7

8 Figure S6. Job plot experiment with a maximum at 0.33 indicating 1:2 stoichiometry for receptor BF 4 - and H 2 PO 4 - in CD 3 CN/CD 3 OD (9/1, v/v). Table S1. Experimental NMR diffusion coefficients D (10-9 m 2 s -1 ) recorded as a function of the concentration of the bis-iodotriazolium receptor BF - 4 and the species H 2 PO - 4, 1 2+ SO 2-4 and 1 2+ HP 2 O 3-7 measured in CD 3 CN/CD 3 OD (9:1 v/v). C BF HP 3-2 O H - 2 PO SO 2-4 (mm) Figure S7. Effects of the concentration on the diffusion coefficients of the receptor BF 4 - (black) and the species H 2 PO 4 -, 1 2+ SO 4 2- and 1 2+ HP 2 O 7 3- measured in CD 3 CN/CD 3 OD (9:1 v/v). Figure S8. Comparison of the 1 H NMR spectra in CD 3 CN/CD 3 OD (9:1 v/v) at 20ºC of the monomer a) BF 4 -, b) BF 4 - /H 2 PO 4 - complex, c) BF 4 - /H 2 PO 4 - complex after addition of Zn 2+. S8

9 PART III: Cooperative model analyses. In order to elaborate the cooperative model used to describe the thermodynamcis of the formation of the heteromonomer supramolecular polymers we have used the same strategy previously applied [2] to describe the polymerization of a single monomer. The cooperative model is composed of one initial nucleation equilibrium followed by sucessive elongation steps where A, B and (AB) i denote the two monomers and the supramolecular polymer of length i, and K N and K E are the equilibrium constants for the nucleation and elongation steps. The nucleation step is usually less favoured that the elongation steps so that K N << K E, and the elongation equilibrium constants are considered to have the same value. From Equation (1) we can express the concentration of the polymers in terms of [A] and [B] as follows The total concentration of A (C A ) is then given by where the identity S9

10 was used in the last step. Following a similar procedure we obtain We note that from Equations (3) and (4) we can also derive which is a direct consequence from the stechiometry of Equation (1). Equations (3) and (4) stablish the relationship between the total concentration of A and B (C A and C B ), quantities decided at the begining of the experiment, and their values at equilibrium ([A] and [B]), quantities directly related to the meassurement of some experimental quantity, the NMR shift in our present study. Consequently they can be used to obtain through a nonlinear curve fitting analysis the values of the K N and K E equilibrium constants of the model that better reproduce the experimental data. S10

11 PART IV: SEM images. Figure S9. Six different SEM images of the self-assembled compounds H 2 PO 4 -. S11

12 Figure S10. Six different SEM images of the self-assembled compounds SO S12

13 PART V: X-ray Table S2. Crystal data and structure refinement for 1 2+ SO 2-4. Identification code 1 2+ SO 2-4 Empirical formula C36 H39 I2 N9 O12 S Formula weight Temperature 100(2) K Wavelength Å Crystal system Monoclinic Space group P2 1 /n Unit cell dimensions a = (9) Å α= 90. b = (11) Å β= (3). c = (3) Å γ = 90. Volume (6) Å 3 Z 4 Density (calculated) Mg/m3 Absorption coefficient mm-1 F(000) 2144 Crystal size x x mm 3 Theta range for data collection to Index ranges -13<=h<=13, -15<=k<=15, -41<=l<=41 Reflections collected Independent reflections 8911 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 8911 / 117 / 609 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S13

14 Figure S11. X-ray structure of 1 2+ SO 4 2-.Thermal ellipsoids are drawn at the 50% probability level Figure S12. Powder X-ray Diffraction patterns of 1 2+ SO S14

15 PART VI: Fluorescence Anion Binding Studies Figure S13. Emission spectrum of the compound BF 4 - (black) after the addition up to 8 equiv of SO 4 2- (blue), HP 2 O 7 3- (green) and H 2 PO 4 - (red) anions. Figure S14. Changes in the fluorescence spectra of compound BF 4 - (c = 2.5 x 10-4 M in CH 3 CN/CH 3 OH 9:1) (black) upon addition of increasing amounts of H 2 PO 4 anions at 20 C. Figure S15. Changes in the fluorescence spectra of compound BF 4 - (c = 2.5 x 10-4 M in CH 3 CN/CH 3 OH 9:1) (black) upon addition of increasing amounts of HP 2 O 7 3 anions at 20 C. S15

16 Part VI: 1H-NMR titration experiment of the proto-triazolium analogue Figure S16. 1 H NMR spectral changes observed in proto-triazolium analoge in CD 3 CN/CD 3 OD (9:1, v/v) during the addition of HP 2 O 7 3- ions. S16

17 Figure S17. 1 H NMR spectral changes observed in proto-triazolium analoge in CD 3 CN/CD 3 OD (9:1, v/v) during the addition of H 2 PO 4 - ions. S17

18 References (1) Sheldrick, G.M. Acta Cryst. 2015, C71, 3-8 (2) Zhao, D.; Moore, J. Org. Biomol. Chem. 2003, 1, S18