Supporting Information. A Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair. Receptor for the Recognition and Extraction of Lithium Nitrite

Supporting Information For A Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite Qing He, Zhan Zhang, James T. Brewster, Vincent M. Lynch, Sung Kuk Kim *, and Jonathan L. Sessler * Department of Chemistry, The University of Texas at Austin, 105 East 24th, Street-Stop A5300, Austin, Texas 78712-1224, United States Institute for Supramolecular and Catalytic Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China Department of Chemistry and Research Institute of National Science, Gyeongsang National University, Jinju, 660-701, Korea * Corresponding author: Jonathan L. Sessler (E-mail: sessler@mail.utexas.edu), Sung Kuk Kim (E-mail: sungkukkim@gnu.ac.kr) 1. General Information 2. Synthesis 3. Crystal structure of 1 LiCl Contents 4. 1 H NMR spectroscopic titrations of receptor 1 with LiClO4 or NaClO4 5. DFT calculations 6. 1 H NMR spectral titrations used to determine binding constants 7. Proposed LiNO2 complexation pathways for 1 8. X-ray Experimental 9. References 10. Energies and geometrical coordinates of the optimized models in the gas phase 11. Additional high resolution mass spectra and NMR spectra S1

1. General Information All solvents and chemicals used were purchased from Aldrich, TCI, and Acros and used without further purification. TLC analyses were carried out by using Sorbent Technologies silica gel (200 mm) sheets. Column chromatography was performed on Sorbent silica gel 60 (40 63 mm). NMR spectra were recorded on a Varian Mercury 400 instrument. The NMR spectra were referenced to solvent residue peaks and the spectroscopic solvents were purchased from Cambridge Isotope Laboratories and Aldrich. Electrospray ionization (ESI) mass spectra were recorded on a VG AutoSpec apparatus. X-ray crystallographic analyses were carried out on either a Rigaku AFC12 diffractometer equipped with a Saturn 724+ CCD or an Agilent Technologies SuperNova Dual Source diffractometer using a µ-focus Cu Kα radiation source (λ = 1.5418Å) with collimating mirror monochromators. A graphite monochromator and MoKα radiation were used. Further details of the structures and their refinement is given in a later section. 2. Synthesis Scheme S1. Synthesis of intermediate 2. Compounds s1, s3 and s5 were commercially available and s2, s4 were prepared according to literature reports. 1 6, 6'-(2-Methoxy-1, 3-phenylene)bis(pyridin-2-amine) (2) Compounds s4 (1.80 g, 5mmol), s5 (1.73 g, 10 mmol), Pd(PPh 3) 4 (346 mg, 0.3 mmol), and K 3PO 4 (6.36 g, 30 mmol) were mixed and dissolved in dry DMF (60 ml) and then heated to 110 under an N 2 atmosphere and then stirred for 5 h. After allowing the reaction mixture to cool to room temperature, the mixture was diluted with ethyl acetate (150 ml). The resulting solution was washed with water (5 60 ml). The combined organic phase was dried over anhydrous Na 2SO 4 for 4 h. After evaporation of the solvent, the residue was subjected to flash column over silica gel eluting with dichloromethane/methanol/triethylamine (100:4:1) to obtain the products (0.92 g, 63%) as an off-white solid. 1 H NMR (400 MHz, CD 3OD): δ 7.55-7.48 (m, 4H, ArH), 7.28-7.22 (t, J = 8.0 Hz, 1H, ArH), 7.00-6.97 (dd, J = 8.0 Hz, 0.8 Hz, 2H, ArH), 6.58-6.53 (dd, J = 8.0 Hz, 0.8 Hz, 2H, ArH), 3.33 (s, 3H, OMe); 13 C NMR (100 MHz, CD 3OD): δ 160.8, 157.0, 155.5, 139.3, 136.0, 132.2, 124.9, 115.0, 108.6, 61.8; HRMS (ESI) m/z 293.1397 [M + H] + calcd for C 17H 17N 4O, found 293.1404. S2

Scheme S2. Synthesis of intermediate 3. 4, 4-Di(1H-pyrrol-2-yl)pentanoic acid (3): A mixture of levulinic acid s6 (30.01 g, 259 mmol) and pyrroles s7 (80.05 g, excess) were dissolved in Et 2O (400 ml). Methanesulfonic acid (1.5 ml) was added dropwise, then stirred at room temperature overnight. The mixture was washed with water (8 200 ml) and the organic phase was separated and dried over anhydrous Na 2SO 4. The solvent was removed under reduced pressure and the resulting residue was subjected to flash column over silica gel using dichloromethane (DCM) as the eluent, obtaining the product 3 as white solid (11.48 g, 19%). 1 H NMR (400 MHz, CD 3OD): δ 9.66 (brs., 2H, NH), 6.63-6.61 (m, 2H, pyrrole-h), 6.01-5.98 (m, 2H, pyrrole-h), 5.95-5.92 (m, 2H, pyrrole-h), 2.33-2.27 (m, 2H, CH 2), 2.17-2.11 (m, 2H, CH 2), 1.57 (s, 3H, CH 3); 13 C NMR (100 MHz, CD 3OD): δ 178.9, 139.7, 118.9, 108.6, 106.2, 40.7, 38.2, 31.8, 27.3; HRMS (ESI) m/z 255.1104 [M + Na] + calcd for C 13H 16N 2NaO 2, found 255.1103. Synthesis of precursor 4: To a mixture of compound 2 (1.15 g, 3.9 mmol), 3 (2.26 g, 9.7 mmol), and EDCI HCl (2.50 g, 13.0 mmol) in DCM (120 ml) 5 ml of pyridine was added. The resulting solution was stirred at room temperature under an N 2 atmosphere for 36 h. After the DCM was removed under reduced pressure, the residue was subjected to silica gel column eluting with ethyl acetate/hexanes (1/3, v/v) to give 2.31 g (81% yield) of 4 as thick oil. 8.16 (s, 2H, CONH), 8.12-7.98 (m, 6H), 7.76 (t, J = 8.0 Hz, 2H, ArH), 7.65-7.63 (d, J = 8.0 Hz, 2H, ArH), 7.57-7.55 (dd, J = 8.0 Hz, 4.0 Hz, 1H, ArH), 6.65-6.56 (m, 4H, pyrrole-h), 6.17-5.98 (m, 8H, pyrrole-h), 3.27 (s, 3H, OMe), 2.43-2.35 (m, 4H, CH 2), 2.27-2.17 (m, 4H, CH 2), 1.57 (s, 6H, CH 3); 13 C NMR (100 MHz, CD 2Cl 2): δ 173.0, 157.3, 155.6, 152.3, 139.7, 138.3, 134.9, 132.8, 125.3, 121.6, 118.4, 113.3, 108.9, 106.0, 62.6, 39.9, 37.1, 34.3, 27.2; HRMS (ESI) m/z 743.3429 [M + Na] + calcd for C 43H 44N 8NaO 3, found 743.3436. Synthesis of compound 1: BF 3 Et 2O (0.8 ml) was added dropwise to a solution of precursor 4 (2.61 g, 3.6 mmol) in acetone (1000 ml) at RT. The reaction solution was stirred at RT overnight. Then triethylamine (20 ml) was added to quench the reaction. The solvent was removed and the resulting residue was purified by column chromatography over silica gel (eluent: ethyl acetate/hexanes (1/3, v/v)) to give 0.55 g (19% yield) of 1 as an off-white solid. 1 H NMR (400 MHz, CD 2Cl 2): δ 8.27-8.00 (m, 8H), 7.88-7.83 (t, J = 8.0 Hz, 2H, ArH), 7.46-7.44 (d, J = 8.0 Hz, 2H, ArH), 7.33-7.31 (d, J = 8.0 Hz, 2H, ArH), 7.26 (t, J = 8.0 Hz, 1 H, ArH), 5.96-5.89 (m, 8H, pyrrole-h), 3.22 (s, 3H, OMe), 2.38-2.26 (m, 8H, CH 2), 1.57-1.46 (m, 18H, Me); 13 C NMR (100 MHz, CD 2Cl 2): δ 173.3, 157.2, 157.0, 152.0, 140.7, 140.2, 137.8, 135.4, 132.4, S3

124.8, 120.1, 113.7, 105.5, 104.5, 62.3, 40.3, 38.2, 36.5, 35.3, 31.7, 29.6, 29.0; HRMS (ESI) m/z 823.4055 [M + Na] + calcd for C 49H 52N 8NaO 3, found 823.4059. 3. Crystal structure of 1 LiCl Figure S1. Single crystal X-ray diffraction structures of compound 1 obtained from the evaporation of solutions of A) acetonitrile; B) a mixture of ethyl acetate and methanol and C) a mixture of chloroform and methanol. Three different structures of 1 were obtained from the analysis of single crystals obtained via the slow evaporation of acetonitrile (A), from a mixture of ethyl acetate and methanol (B), and from a mixture of chloroform, acetonitrile and methanol (C). In all three cases, the calix[4]pyrrole was found to adopt a 1,2-alternate conformation, which differs from that seen for the 0ligoether-strapped calix[4]pyrroles 2 and calix[4]arene-strapped calix[4]pyrroles in the absence of anionic salts. 3 Analysis of Crystal A showed that the cavity formed by the hemispherand was predominantly occupied by a methoxyphenyl group. However, analysis of Crystals B and C revealed the central pockets being occupied by two methanol molecules or two water molecules, respectively. On this basis we inferred that receptor 1 might be sufficiently flexible so as to accommodate lithium salts in the form of ion pairs. S4

Figure S2. A) Front view and B) side view of the single crystal X-ray diffraction structure of the lithium complex [1 LiCl H 2O MeOH].This crystal of the complex 1 LiCl H 2O MeOH was obtained by allowing a mixture of receptor 1 and excess lithium chloride, sodium chloride, potassium chloride, and rubidium chloride in CHCl 3/CH 3CN/CH 3OH to undergo slow evaporation. Key metric parameters are: 1.885 Å for Li1 O1, 2.110 Å for Li1 N7, 2.110 Å for Li1 N7, 3.207 Å for Li1 O2, 4.298 Å for Li1 N6, and 4.337 Å for Li1 Cl1, respectively. 4. 1 H NMR spectroscopic titrations of receptor 1 with LiClO4 or NaClO4 Figure S3. 1 H NMR titration of receptor 1 with LiClO 4 in a mixed solvent consisting of CD 2Cl 2/CD 3OD (9/1, v/v). The concentration of 1 was 5.0 mm. S5

Figure S4. 1 H NMR titration of receptor 1 with NaClO 4 in a mixed solvent consisting of CD 2Cl 2/CD 3OD (9/1, v/v). The concentration of 1 was 5.0 mm. 5. DFT calculations All geometrical optimizations and frequency analyses were carried out with the Gaussian09 suite 4 of programs at the B3LYP/6-31G*//B3LYP/6-31G* level. Frequency analyses were run to confirm that all the structures obtained were local minima. Figure S5. DFT optimized molecular models of the complexes of receptor 1 with (A) LiCl and (B) LiCl H 2O. S6

Figure S6. DFT optimized molecular models of the complexes of receptor 1 with (A) NaCl and (B) NaCl H 2O. Figure S7. DFT optimized molecular models of the complexes of receptor 1 with (A) KCl and (B) KCl H 2O. S7

Figure S8. DFT optimized molecular models of the complexes of receptor 1 with (A) LiBr; (B) LiNO 2 and (C) LiNO 3. Table S1. Calculated Gas-Phase Binding Distances and Energies for Two Possible Ion Pair Complexes of 1. Table S2. Calculated Gas-Phase Binding Distances and Energy for four Ion Pair complexes of 1. 6. 1 H NMR spectral titrations used to determine binding constants S8

Figure S9. Stacked 1 H NMR spectra corresponding to the titration of 1 (5.0 mm) with LiCl (0.9 M) in a mixture of CD 2Cl 2/CD 3OD (9/1, v/v). Figure 10. Binding curve obtained by fitting the chemical shift change of the pyrrole NH signal against [LiCl]. K a = 45 ± 1 M -1.. S9

1.25 1.00 Titration Fitting Curve y =(1+a*K+x*K-sqrt(-4*a*x*K^2+(-1-a*K-x*K)^2))/(2*K)*(dd)/a 0.75 Δδ (ppm) 0.50 0.25 0.00 a a K K dd dd Statisti Statisti Value Error Value Error Value Error Reduc Adj. R- deltah 0.005 0 73.89 8.284 1.081 0.039 7.774 0.990 0.00 0.02 0.04 0.06 0.08 0.10 C(LiCl)/M Figure S11. Binding curve obtained by fitting the chemical shift change of the pyrrole NH signal against [LiBr]. K a = 74 ± 8 M -1. Titration Fitting Curve 1.50 y =(1+a*K+x*K-sqrt(-4*a*x*K^2+(-1-a*K-x*K)^2))/(2*K)*(dd)/a 1.25 Δδ (ppm) 1.00 0.75 0.50 0.25 a a K K dd dd Statis Statis Value Error Value Error Value Error Redu Adj. R delta 0.005 0 107.7 7.455 1.441 0.020 7.674 0.996 0.00 0.00 0.03 0.06 0.09 0.12 0.15 C(LiNO 2 )/M Figure S12. Binding curve obtained by fitting the chemical shift change of the pyrrole NH signal against [LiNO 2]. K a = 108 ± 7 M -1. S10

1.5 Titration Fitting Curve y =(1+a*K+x*K-sqrt(-4*a*x*K^2+(-1-a*K-x*K)^2))/(2*K)*(dd)/a 1.2 0.9 Δδ (ppm) 0.6 0.3 a a K K dd dd Statist Statist Value Error Value Error Value Error Reduc Adj. R deltah 0.005 0 263.3 12.62 1.279 0.011 1.846 0.998 0.0 0.00 0.02 0.04 0.06 0.08 0.10 C(LiNO 3 )/ M Figure S13. Binding curve obtained by fitting the chemical shift change of the pyrrole NH signal against [LiNO 3]. K a = 263 ± 13M -1. Figure S14. 1 H NMR spectroscopic titration of receptor 1 with LiNO 2 in a mixed solvent consisting of CD 2Cl 2/CD 3OD (9/1, v/v). The concentration of 1 was 5.0 mm. S11

Figure S15. 1 H NMR titration of receptor 1 with TBANO 2 in a mixture solvent of CD 2Cl 2/CD 3OD (9/1, v/v). The concentration of 1 was 5.0 mm. S12

Figure S16. Top: 1 H NMR titration of receptor 1 with lithium tetraphenylborate (LiTPB) in a mixed solvent consisting of CD 2Cl 2/CD 3OD (9/1, v/v). Bottom: 1 H NMR spectroscopic titration of receptor 1 and 20 equiv of LiTBP with TBANO 2 in a mixed solvent system consisting of CD 2Cl 2/CD 3OD (9/1, v/v). The concentration of 1 was 5.0 mm. 7. Proposed LiNO2 complexation pathways for 1 Figure S17. Proposed LiNO 2 complexation pathways for 1. S13

8. X-ray Experimental X-ray experimental for the complex of 1 LiCl (right) Single crystals of C54H69ClLiN9O7 [1 LiCl] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3CN/CH3OH solution of receptor 1 in the presence of excess lithium chloride. A suitable crystal was selected and the data were collected on a Rigaku AFC12 diffractometer with a Saturn 724+ CCD using a graphite. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483285. Figure S18. View of complex of 1 LiCl. Displacement ellipsoids are scaled to the50% probability level. S14

Table S3 Crystal data and structure refinement for 1 LiCl Empirical formula C54H69ClLiN9O7 Formula weight 998.57 Temperature/K 100.15 Crystal system triclinic Space group P-1 a/å 10.850(5) b/å 13.688(6) c/å 18.213(8) α/ 85.376(11) β/ 88.134(14) γ/ 89.723(11) Volume/Å 3 2695(2) Z 2 ρcalcg/cm 3 1.231 μ/mm -1 0.130 F(000) 1064.0 Crystal size/mm 3 0.179 0.093 0.090 Radiation MoKα (λ = 0.71075) 2Θ range for data collection/ 2.986 to 62.5 Index ranges -15 h 15, -19 k 18, -25 l 25 Reflections collected 39913 Independent reflections 15033 [Rint = 0.1045, Rsigma = 0.1410] Data/restraints/parameters 15033/0/693 Goodness-of-fit on F 2 1.197 Final R indexes [I>=2σ (I)] R1 = 0.1309, wr2 = 0.2608 Final R indexes [all data] R1 = 0.1971, wr2 = 0.3001 Largest diff. peak/hole / e Å -3 0.61/-0.68 CCDC Number 1483285. S15

X-ray experimental for the complex of 1 LiCl (left) Single crystals of C54H69ClLiN9O7 [1 LiCl] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3CN/CH3OH solution of receptor 1 in the presence of excess lithium chloride, sodium chloride, potassium chloride and rubidium chloride. A suitable crystal was selected and the data were collected on an Agilent Technologies SuperNova Dual Source diffractometer using a µ-focus Cu Kα radiation source (λ = 1.5418Å) with collimating mirror monochromators. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483286. Figure S19. View of complex of 1 LiCl. Displacement ellipsoids are scaled to the50% probability level. S16

Table S4 Crystal data and structure refinement for 1 LiCl Empirical formula C54H69ClLiN9O7 Formula weight 998.57 Temperature/K 100.15 Crystal system triclinic Space group P-1 a/å 10.8528(2) b/å 13.6605(3) c/å 18.1919(3) α/ 85.4609(14) β/ 88.1007(15) γ/ 89.6809(17) Volume/Å 3 2687.08(9) Z 2 ρcalcg/cm 3 1.234 μ/mm -1 1.104 F(000) 1064.0 Crystal size/mm 3 0.115 0.055 0.052 Radiation CuKα (λ = 1.54184) 2Θ range for data collection/ 4.876 to 147.366 Index ranges -13 h 13, -16 k 16, -22 l 22 Reflections collected 51033 Independent reflections 10647 [Rint = 0.0324, Rsigma = 0.0235] Data/restraints/parameters 10647/435/673 Goodness-of-fit on F 2 1.036 Final R indexes [I>=2σ (I)] R1 = 0.0394, wr2 = 0.1012 Final R indexes [all data] R1 = 0.0427, wr2 = 0.1040 Largest diff. peak/hole / e Å -3 0.87/-0.37 CCDC number 1483286 S17

X-ray experimental for the complex of 1 LiBr Single crystals of C56 H65 Br Li N11 O4 [1 LiBr] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3CN/CH3OH solution of receptor 1 in the presence of excess lithium bromide. A suitable crystal was selected and the data were collected on a Rigaku AFC12 diffractometer with a Saturn 724+ CCD using a graphite. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483281. Figure S20. View of complex of 1 LiBr. Displacement ellipsoids are scaled to the50% probability level. S18

Table S5 Crystal data and structure refinement for 1 LiBr Empirical formula C56H65BrLiN11O4 Formula weight 1043.04 Temperature/K 100.1500 Crystal system triclinic Space group P-1 a/å 13.8555(8) b/å 13.8676(8) c/å 14.7764(8) α/ 83.160(2) β/ 86.479(2) γ/ 69.655(2) Volume/Å 3 2642.5(3) Z 2 ρcalcg/cm 3 1.311 μ/mm -1 0.835 F(000) 1096.0 Crystal size/mm 3 0.2 0.2 0.2 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/ 6.094 to 50.054 Index ranges -16 h 16, -16 k 16, -17 l 17 Reflections collected 36071 Independent reflections 9281 [Rint = 0.0436, Rsigma = 0.0415] Data/restraints/parameters 9281/42/684 Goodness-of-fit on F 2 1.057 Final R indexes [I>=2σ (I)] R1 = 0.0424, wr2 = 0.1060 Final R indexes [all data] R1 = 0.0488, wr2 = 0.1091 Largest diff. peak/hole / e Å -3 0.81/-0.49 CCNC number 1483281 S19

X-ray experimental for the complex of 1 LiI Single crystals of C56H65ILiN11O4 [1 LiI] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3CN/CH3OH solution of receptor 1 in the presence of excess lithium Iodide. A suitable crystal was selected and the data were collected on an Agilent Technologies SuperNova Dual Source diffractometer using a µ-focus Cu Kα radiation source (λ = 1.5418Å) with collimating mirror monochromators. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483282. Figure S21. View of complex of 1 LiI. Displacement ellipsoids are scaled to the50% probability level. S20

Table S6 Crystal data and structure refinement for complex of 1 LiI Empirical formula C56H65ILiN11O4 Formula weight 1090.03 Temperature/K 100.1500 Crystal system triclinic Space group P-1 a/å 13.8691(14) b/å 13.9169(14) c/å 14.7837(14) α/ 87.019(3) β/ 83.805(3) γ/ 69.563(3) Volume/Å 3 2657.9(5) Z 2 ρcalcg/cm 3 1.362 μ/mm -1 0.659 F(000) 1132.0 Crystal size/mm 3 0.2 0.2 0.2 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/ 6.108 to 50.054 Index ranges -16 h 16, -16 k 16, -17 l 17 Reflections collected 36236 Independent reflections 9391 [Rint = 0.0505, Rsigma = 0.0461] Data/restraints/parameters 9391/471/679 Goodness-of-fit on F 2 1.071 Final R indexes [I>=2σ (I)] R1 = 0.0426, wr2 = 0.1023 Final R indexes [all data] R1 = 0.0483, wr2 = 0.1050 Largest diff. peak/hole / e Å -3 1.05/-0.72 CCDC number 1483282 S21

X-ray experimental for the complex of 1 LiNO2 Single crystals of C56 H65 Li N12 O6 [1 LiNO2] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3CN/CH3OH solution of receptor 1 in the presence of excess lithium nitrite. A suitable crystal was selected and the data were collected on an Agilent Technologies SuperNova Dual Source diffractometer using a µ-focus Cu Kα radiation source (λ = 1.5418Å) with collimating mirror monochromators. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483283. Figure S22. View of complex of 1 LiNO 2. Displacement ellipsoids are scaled to the50% probability level. S22

Table S7 Crystal data and structure refinement for HQ-2N-calixpyr-LiNO2 Empirical formula C56H65LiN12O6 Formula weight 1009.14 Temperature/K 100.00(10) Crystal system triclinic Space group P-1 a/å 13.8350(3) b/å 13.9110(3) c/å 14.7899(3) α/ 86.6932(19) β/ 83.3607(19) γ/ 69.639(2) Volume/Å 3 2650.24(11) Z 2 ρcalcg/cm 3 1.265 μ/mm -1 0.678 F(000) 1072.0 Crystal size/mm 3 0.206 0.157 0.101 Radiation CuKα (λ = 1.54184) 2Θ range for data collection/ 6.018 to 147.008 Index ranges -17 h 17, -17 k 17, -18 l 18 Reflections collected 49679 Independent reflections 10482 [Rint = 0.0341, Rsigma = 0.0192] Data/restraints/parameters 10482/453/690 Goodness-of-fit on F 2 1.024 Final R indexes [I>=2σ (I)] R1 = 0.0416, wr2 = 0.1043 Final R indexes [all data] R1 = 0.0430, wr2 = 0.1054 Largest diff. peak/hole / e Å -3 0.73/-0.65 CCDC number 1483283 S23

X-ray experimental for the complex of 1 LiNO3 Single crystals of C51 H60 Li N9 O8 [1 LiNO3] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3CN/CH3OH solution of receptor 1 in the presence of excess lithium nitrate. A suitable crystal was selected and the data were collected on a Rigaku AFC12 diffractometer with a Saturn 724+ CCD using a graphite. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483284. Figure S23 View of complex of 1 LiNO 3. Displacement ellipsoids are scaled to the50% probability level. S24

Table S8 Crystal data and structure refinement for the complex of 1 LiNO3 Empirical formula C51H60LiN9O8 Formula weight 934.03 Temperature/K 100.15 Crystal system monoclinic Space group P21/c a/å 14.7928(9) b/å 12.3477(7) c/å 27.0073(16) α/ 90 β/ 98.997(2) γ/ 90 Volume/Å 3 4872.4(5) Z 4 ρcalcg/cm 3 0.938 μ/mm -1 0.066 F(000) 1472.0 Crystal size/mm 3 0.194 0.104 0.091 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/ 6.11 to 50.054 Index ranges -17 h 17, -14 k 14, -32 l 32 Reflections collected 64398 Independent reflections 8592 [Rint = 0.0916, Rsigma = 0.0644] Data/restraints/parameters 8592/417/635 Goodness-of-fit on F 2 1.039 Final R indexes [I>=2σ (I)] R1 = 0.0861, wr2 = 0.2014 Final R indexes [all data] R1 = 0.1271, wr2 = 0.2241 Largest diff. peak/hole / e Å -3 0.91/-0.80 CCDC number 1483284 S25

X-ray experimental for 1 2H2O Single crystals of C50 H60 N8 O6 [1 2H2O] were obtained as colorless blocks via the slow evaporation of a CHCl3/CH3OH solution of receptor 1. A suitable crystal was selected and the data were collected on a Rigaku AFC12 diffractometer with a Saturn 724+ CCD using a graphite. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483287. Figure S24. View of complex of 1 2H 2O. Displacement ellipsoids are scaled to the50% probability level. S26

Table S9 Crystal data and structure refinement for 1 2H2O Empirical formula C64HClLiN4O4 Formula weight 869.06 Temperature/K 100.1500 Crystal system triclinic Space group P-1 a/å 9.700(2) b/å 12.142(3) c/å 20.293(5) α/ 93.671(15) β/ 101.175(7) γ/ 102.189(7) Volume/Å 3 2278.0(9) Z 2 ρcalcg/cm 3 1.347 μ/mm -1 0.142 F(000) 922.0 Crystal size/mm 3 0.2 0.2 0.2 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/ 3.452 to 55.144 Index ranges -12 h 12, -13 k 15, -25 l 26 Reflections collected 18914 Independent reflections 10304 [Rint = 0.0339, Rsigma = 0.0607] Data/restraints/parameters 10304/384/592 Goodness-of-fit on F 2 1.029 Final R indexes [I>=2σ (I)] R1 = 0.0680, wr2 = 0.1684 Final R indexes [all data] R1 = 0.0910, wr2 = 0.1879 Largest diff. peak/hole / e Å -3 1.22/-1.06 CCDC number 1483287 S27

X-ray experimental for 1 2CH3OH Single crystals of C105 H136 N16 O15 [1 2CH3OH] were obtained as colorless blocks via the slow evaporation of an Ethyl acetate/ch3oh solution of receptor 1. A suitable crystal was selected and the data were collected on a Rigaku SCX-Mini diffractometer with a Mercury CCD using a graphite. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483288. Figure S25. View of complex of 1 2CH 3OH. Displacement ellipsoids are scaled to the50% probability level. S28

Table S10 Crystal data and structure refinement for 1 2CH3OH Empirical formula C48H28N6O4Cl0.17 Formula weight 1862.30 Temperature/K 100.1500 Crystal system triclinic Space group P-1 a/å 11.3956(6) b/å 20.1626(11) c/å 23.5767(13) α/ 110.412(2) β/ 99.661(2) γ/ 90.596(2) Volume/Å 3 4991.0(5) Z 6 ρcalcg/cm 3 1.514 μ/mm -1 0.112 F(000) 2357.0 Crystal size/mm 3 0.2 0.2 0.2 Radiation MoKα (λ = 0.71075) 2Θ range for data collection/ 6.03 to 54.97 Index ranges -14 h 14, -26 k 26, -30 l 30 Reflections collected 81581 Independent reflections 22854 [Rint = 0.1150, Rsigma = 0.1437] Data/restraints/parameters 22854/810/1258 Goodness-of-fit on F 2 1.042 Final R indexes [I>=2σ (I)] R1 = 0.1088, wr2 = 0.2048 Final R indexes [all data] R1 = 0.2002, wr2 = 0.2481 Largest diff. peak/hole / e Å -3 1.31/-1.22 CCDC number 1483288 S29

X-ray experimental for 1 CH3CN Single crystals of C102 H112 N18 O7 [1 CH3CN] were obtained as colorless blocks via the slow evaporation of an acetonitrile solution of receptor 1. A suitable crystal was selected and the data were collected on a Rigaku SCX-Mini diffractometer with a Mercury CCD using a graphite. The crystal was kept at 100.15 K during data collection. Using Olex2 5, the structure was solved with the ShelXT 6 structure solution program using Direct Methods and refined with the ShelXL 7 refinement package using Least Squares minimisation. Tables of positional and thermal parameters, bond lengths and angles, torsion angles and figures are in the CIF. CCDC deposition number: 1483352. Figure S26. View of complex of 1 CH 3CN. Displacement ellipsoids are scaled to the50% probability level. S30

Table S11 Crystal data and structure refinement for 1 CH3CN Empirical formula C102 H112 N18 O7 Formula weight 1702.10 Temperature/K 153.1500 Crystal system triclinic Space group P-1 a/å 13.9316(19) b/å 18.999(3) c/å 20.790(3) α/ 113.997(3) β/ 97.902(4) γ/ 97.286(4) Volume/Å 3 4877.0(12) Z 6 ρcalcg/cm 3 1.172 μ/mm -1 0.089 F(000) 1831.0 Crystal size/mm 3 0.65 0.21 0.1 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/ 5.97 to 54.968 Index ranges -18 h 17, -23 k 24, -26 l 26 Reflections collected 57056 Independent reflections 21702 [Rint = 0.1536, Rsigma = 0.3139] Data/restraints/parameters 21702/0/1163 Goodness-of-fit on F 2 0.993 Final R indexes [I>=2σ (I)] R1 = 0.1161, wr2 = 0.3339 Final R indexes [all data] R1 = 0.2529, wr2 = 0.3892 Largest diff. peak/hole / e Å -3 2.55/-0.52 CCDC number 1483352 S31

9. REFERENCES (1). Chan, Julian M.W.; Swager, Timothy M. Tetrahedron Lett. 2008, 49, 4912. (2). (a) Park, I. W.; Yoo, J.; Kim, B.; Adhikari, S.; Kim, S. K.; Yeon, Y.; Haynes, C. J. E.; Sutton, J. L.; Tong, C. C.; Lynch, V. M.; Sessler, J. L.; Gale, P. A.; Lee, C. H. Chem. -Eur. J. 2012, 18, 2514; (b) Park, I. W.; Yoo, J.; Adhikari, S.; Park, J. S.; Sessler, J. L.; Lee, C. H. Chem. Eur. J. 2012, 18, 15073. (3). Kim, S. K.; Sessler, J. L. Acc. Chem. Res. 2014, 47, 2525-2536. (4). Gaussian 09, Revision E.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; and Fox, D. J., Gaussian, Inc., Wallingford CT, 2009. (5). Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H. (2009), J. Appl. Cryst. 42, 339-341. (6). Sheldrick, G.M. Acta Cryst. 2015, A71, 3. (7). Sheldrick, G.M. Acta Cryst. 2015, C71, 3. S32

10. Energies and geometrical coordinates of the optimized models in the gas phase Receptor 1 E(RB3LYP): -2562.23686 a.u. Number of negative frequencies: 0 Cartesian coordinates: Symbol X Y Z C -1.65324800-1.94313100 2.44984500 C -2.78641600-2.72623400 2.56830500 H -3.46341500-2.73604300 3.41151600 C -2.91071600-3.49831800 1.38065200 H -3.69014600-4.21761300 1.16595900 C -1.85460200-3.17016300 0.54524400 C -1.57809300-3.60019400-0.88906900 C -2.32589200-2.68319300-1.85549500 C -2.04430000-2.28054200-3.14903200 H -1.16871800-2.54663700-3.72509900 C -3.11547500-1.45069800-3.59107400 H -3.19912900-0.97667500-4.55950700 C -4.03523100-1.36315800-2.56273400 C -5.37236600-0.65206200-2.44397900 C -5.41428000 0.13848300-1.14831700 C -6.33007200 0.18479700-0.11410300 H -7.23834700-0.39809000-0.04609300 C -5.86982800 1.13783500 0.83640700 H -6.34944600 1.39337800 1.77150200 C -4.67752000 1.66445500 0.37502900 C -3.73854100 2.67336100 1.03319100 C -3.04538000 2.01954400 2.21817300 C -2.83336100 2.43519800 3.51942900 H -3.17476700 3.36555800 3.95252400 C -2.09281200 1.41692400 4.18981500 H -1.76310500 1.44163500 5.21957600 C -1.86273600 0.39656600 3.28687800 C -1.07718500-0.90429500 3.40441600 C -2.06589000-5.05755300-1.09244900 H -1.55438900-5.74829000-0.41213200 H -1.87837400-5.37150100-2.12482900 H -3.14154500-5.14325300-0.91288300 C -6.51833900-1.69217200-2.45290900 H -6.48562700-2.27073700-3.38138600 H -7.49388600-1.19733800-2.38738800 S33

H -6.43332100-2.39076800-1.61426100 C -5.56879900 0.29740300-3.64965200 H -4.77810500 1.05312500-3.70260700 H -6.52860200 0.81573400-3.56092700 H -5.56449000-0.26319600-4.59119200 C -4.58000400 3.87554900 1.51601600 H -5.37299300 3.54691200 2.19246300 H -5.04577800 4.37600200 0.66080300 H -3.96846900 4.60634900 2.05342800 C -1.17596900-1.43626200 4.85165700 H -2.21344300-1.63040300 5.13862600 H -0.76268900-0.70780100 5.55736300 H -0.60816500-2.36713600 4.95115100 C 0.41385700-0.61958900 3.08954500 H 1.01615800-1.53310600 3.13510700 H 0.80829700 0.09484400 3.81871700 H 0.54858000-0.17872600 2.09696900 C -0.06863400-3.50440300-1.23424600 H 0.06848300-3.85809000-2.26134700 H 0.21547800-2.44854800-1.23558500 C 0.88717800-4.28285700-0.29484800 H 0.36513700-4.55116100 0.63170300 H 1.22443500-5.21839400-0.75538100 C 2.05419000-3.38274600 0.10946000 C 4.57642500-3.30668800-0.02002700 C 5.71011600-4.13728600-0.06432500 H 5.61425400-5.21866800-0.11480600 C 6.95580000-3.52379300-0.04795800 H 7.86001700-4.12424800-0.09792500 C 7.03539400-2.13382000 0.02532400 H 7.99665200-1.63219700 0.01022800 C 5.84463700-1.39260700 0.09566200 C 5.88246300 0.09141900 0.22519100 C 6.86090400 0.67792200 1.04513500 H 7.55528600 0.03297200 1.57628600 C 6.93209000 2.05609300 1.22408000 H 7.69173400 2.48213300 1.87311000 C 6.00508400 2.88186200 0.59043100 H 6.03573900 3.95791100 0.73889900 C 5.01440400 2.33550000-0.23074200 C 4.96266000 0.94409400-0.42571900 S34

C 3.99608400 3.21777900-0.88468600 C 4.31829900 4.00422200-1.99530400 H 5.32139800 3.98402100-2.40915700 C 3.31580700 4.79914500-2.55530700 H 3.52878100 5.41631600-3.42434300 C 2.03890300 4.80421600-2.00571100 H 1.22981500 5.39874600-2.40578400 C 1.82802100 3.99452500-0.87788100 C -0.59478400 4.53325800-0.45799400 C -1.69395100 4.21814100 0.54924500 H -2.22281300 5.15812700 0.72964700 H -1.27854000 3.87770600 1.50399600 C -2.66850800 3.15847800 0.00162400 H -2.07731000 2.29243700-0.32689100 H -3.17034100 3.56647900-0.88433800 C 4.42428600 0.05514600-2.54921100 H 4.85018400 0.90134100-3.10595800 H 3.53753400-0.31062200-3.07145200 H 5.16745400-0.75020500-2.49409100 N -1.11113300-2.20391500 1.20252700 N -3.54108800-2.12558900-1.52419500 N -4.41541700 1.03917300-0.83013000 N -2.42802700 0.79043600 2.09205400 N 3.30763500-3.91788600-0.11897400 N 4.63724800-1.98385800 0.06406400 N 2.77489400 3.22227200-0.33285500 N 0.61047000 3.92090900-0.18355100 H 0.67025700 3.31480400 0.62625200 O 1.85241200-2.27539400 0.58626200 O 3.98453600 0.46133600-1.25797800 O -0.78644600 5.25338100-1.42963400 H 3.32284000-4.87791000-0.43341400 H -3.94280600-2.17358400-0.59603000 H -2.55080200 0.16751000 1.30564300 H -3.61182700 1.20811800-1.41704600 H -0.16524500-1.93751900 0.93070100 Complex of 1 LiCl E(RB3LYP): -3030.12501760 a.u. Number of negative frequencies: 0 Cartesian coordinates: S35

Symbol X Y Z C -2.84946400-1.14658400 2.98133100 C -3.86009700-1.99659600 3.38695300 H -4.49073900-1.86202200 4.25432800 C -3.92529000-3.07519600 2.46448900 H -4.61441800-3.90738700 2.50582100 C -2.95749300-2.87268500 1.49974500 C -2.58493400-3.72454100 0.29489800 C -3.17602500-3.19395600-1.00450600 C -4.05889100-3.76234700-1.90268700 H -4.54520200-4.72196400-1.79493700 C -4.21100800-2.86257500-2.99521800 H -4.83659000-3.01472000-3.86340500 C -3.41593500-1.75832000-2.75248300 C -3.16102800-0.50237200-3.57560100 C -3.64958100 0.74299900-2.84700000 C -4.83223300 1.44341900-2.97589500 H -5.63695600 1.20739100-3.65783100 C -4.80539000 2.52540500-2.05668000 H -5.58707600 3.25850800-1.91880400 C -3.60690000 2.47878700-1.37057400 C -3.07639500 3.39243900-0.26859200 C -3.27743600 2.78735400 1.11353900 C -4.06313900 3.20352100 2.17063800 H -4.71952000 4.06218200 2.17312000 C -3.85210900 2.30764100 3.25490100 H -4.32361300 2.36078500 4.22596000 C -2.93691700 1.35605600 2.84980700 C -2.35568600 0.15983400 3.59045700 C -3.09206300-5.16215000 0.52279200 H -2.69290200-5.57394600 1.45478300 H -2.79220500-5.80801200-0.30928100 H -4.18311800-5.18603000 0.58879200 C -3.91884100-0.62410000-4.91306700 H -3.56310200-1.49604800-5.47177100 H -3.75510200 0.27137900-5.52011200 H -4.99522000-0.73912700-4.75644900 C -1.64754600-0.38500300-3.89950600 H -1.02474800-0.32289900-3.00067200 H -1.45797100 0.50800400-4.50638200 H -1.32076200-1.26612800-4.46324300 S36

C -3.85747000 4.72231200-0.34369300 H -4.92647000 4.55631200-0.18726300 H -3.72338700 5.18291100-1.32703800 H -3.52076200 5.42506500 0.42264200 C -2.80962800 0.21886800 5.06299000 H -3.89949500 0.19420000 5.14993300 H -2.45367400 1.14255600 5.53017800 H -2.40290000-0.63306200 5.61670600 C -0.80538500 0.22229500 3.57315200 H -0.38333200-0.63326700 4.11296800 H -0.46901100 1.14343200 4.06251100 H -0.39110200 0.21558600 2.56021100 C -1.03884200-3.75094900 0.09431300 H -0.82063200-4.40864100-0.75596800 H -0.70629700-2.75261600-0.20662700 C -0.19835800-4.18372300 1.32663000 H -0.63056500-3.77815600 2.24359400 H -0.15055700-5.27511200 1.41688500 C 1.16774300-3.56697200 1.14833700 C 3.32602300-3.98709600-0.06993600 C 4.08689200-5.01077500-0.65907000 H 3.68175900-6.01287000-0.76398300 C 5.36205600-4.69824800-1.10211600 H 5.97501800-5.45498700-1.58290900 C 5.85181800-3.40694400-0.91178400 H 6.84654900-3.13487700-1.24486300 C 5.03357400-2.45338800-0.29349300 C 5.58322900-1.10781300 0.01971800 C 6.88665700-1.03205000 0.53715900 H 7.43210200-1.95046900 0.73147700 C 7.46404900 0.19571900 0.83559200 H 8.46338000 0.24233600 1.25761300 C 6.74480000 1.36453800 0.60912700 H 7.18370000 2.32381400 0.86445600 C 5.43866200 1.34118300 0.09459900 C 4.86063900 0.08425500-0.18286600 C 4.75053500 2.64329400-0.14295200 C 5.47369000 3.72232500-0.66875000 H 6.51519500 3.60817400-0.94850100 C 4.81150900 4.93738000-0.84577700 H 5.34320100 5.79525900-1.24856900 S37

C 3.46752400 5.05205300-0.52275700 H 2.91076500 5.96872300-0.64887900 C 2.82072700 3.90304800-0.02652200 C 0.53659300 4.89781200 0.23135900 C -0.87854000 4.49371900 0.60399800 H -1.41222500 5.42693700 0.79182600 H -0.88016600 3.91226400 1.53303100 C -1.55974600 3.68166900-0.51774400 H -1.01243000 2.73915200-0.63809900 H -1.46679500 4.21819100-1.47023200 C 3.32998100 0.37122000-2.01948200 H 3.66778600 1.39547200-2.18875500 H 2.25105600 0.30984400-2.16339000 H 3.85294700-0.31545000-2.69523700 Li 2.17606500-1.04831000 0.40040400 N -2.31461300-1.68801400 1.82583700 N -2.79443800-1.97806700-1.54024500 N -2.91714200 1.38054000-1.85942500 N -2.59526000 1.66372700 1.54502700 N 2.03505400-4.30990100 0.37446500 N 3.76606800-2.73491500 0.08297100 N 3.44897800 2.73609800 0.17055700 N 1.46332000 3.86671200 0.29780500 H 1.14022700 2.94134600 0.56452400 O 1.43452500-2.43813000 1.56249600 O 3.56228000-0.02357500-0.65145600 O 0.82664300 6.03575200-0.11242100 H 1.70896400-5.23139300 0.11565400 H -2.16523100-1.32189500-1.09529100 H -1.94314600 1.13245700 0.98075500 H -1.98107300 1.11408000-1.58089100 H -1.51776200-1.30125800 1.33099600 Cl 0.08576800-0.02725300-0.27853500 Complex of 1 NaCl E(RB3LYP): -3184.88595593 a.u. Number of negative frequencies: 0 Cartesian coordinates: Symbol X Y Z C -2.90982000-1.36499300 2.94525200 C -3.78552900-2.35640800 3.34408400 S38

H -4.41329500-2.33044800 4.22327200 C -3.71235900-3.41515600 2.39916900 H -4.27799900-4.33591100 2.42932100 C -2.79577900-3.05951100 1.42832900 C -2.33502600-3.81747800 0.19021500 C -2.98194100-3.29461900-1.08674600 C -3.85576400-3.89948900-1.97005500 H -4.27150500-4.89261000-1.87293500 C -4.10918500-2.98552100-3.03050700 H -4.75235400-3.15995100-3.88136500 C -3.38501700-1.83437700-2.78489200 C -3.24218900-0.55138900-3.59474700 C -3.80627200 0.65327400-2.85186600 C -5.00438000 1.32384600-3.00463400 H -5.78132100 1.07950200-3.71534800 C -5.03305200 2.39226700-2.06782900 H -5.83722100 3.10297100-1.93993500 C -3.85266800 2.36510100-1.34959100 C -3.36417000 3.26327500-0.21589700 C -3.57168600 2.60813600 1.14372500 C -4.43838700 2.92841500 2.17127900 H -5.15517600 3.73740800 2.16810000 C -4.22154000 2.00731700 3.23276300 H -4.74382200 1.99227700 4.17890300 C -3.22200500 1.13623200 2.84452200 C -2.57461600-0.02461200 3.58902200 C -2.70344400-5.30626800 0.35182600 H -2.27486400-5.71849100 1.27007100 H -2.33748400-5.88427500-0.50341500 H -3.78753400-5.43634800 0.40513600 C -4.00953900-0.71635700-4.92181700 H -3.60262000-1.55716200-5.49288400 H -3.91768900 0.19283900-5.52359200 H -5.07290900-0.90625400-4.74926500 C -1.74621600-0.31741100-3.94015300 H -1.11828800-0.21014400-3.04901800 H -1.63460600 0.59152500-4.54248600 H -1.36074900-1.16782900-4.51415300 C -4.17816200 4.57392900-0.25906500 H -5.24414000 4.37847000-0.11570300 H -4.04947900 5.06521200-1.22817500 S39

H -3.86077300 5.26185200 0.52947700 C -3.09598500-0.03258300 5.04025700 H -4.18229200-0.15541000 5.07661900 H -2.84473900 0.91021300 5.53607100 H -2.63977500-0.85492100 5.60018400 C -1.03560600 0.17465400 3.64517700 H -0.56537700-0.64866400 4.19543100 H -0.80272700 1.11606500 4.15597900 H -0.58151600 0.21619600 2.64988700 C -0.78941500-3.69030100 0.00985400 H -0.50889700-4.23921000-0.89764300 H -0.53753700-2.64208200-0.18102500 C 0.06140500-4.18209000 1.21007100 H -0.39780200-3.86628000 2.14956600 H 0.14044900-5.27567700 1.21489800 C 1.42213900-3.52498600 1.12778500 C 3.61508900-3.79018900-0.09852500 C 4.43439200-4.77983000-0.67080800 H 4.07448400-5.79818600-0.78511700 C 5.70857500-4.41826100-1.07834500 H 6.36493600-5.15247100-1.53639000 C 6.13995500-3.10593300-0.88257900 H 7.13196700-2.79143900-1.18693300 C 5.26267400-2.18966500-0.29425600 C 5.72462100-0.80890600 0.01962200 C 6.94441300-0.64287100 0.69291600 H 7.52218200-1.52224600 0.96191000 C 7.39509600 0.62470000 1.04708600 H 8.33356200 0.74101800 1.58072200 C 6.61769300 1.74065500 0.74964200 H 6.94212900 2.72650800 1.06872000 C 5.38996400 1.62157200 0.08039600 C 4.96984900 0.33409000-0.30637800 C 4.58599800 2.85311500-0.17062000 C 5.22083800 4.00411000-0.64905300 H 6.27714200 3.98826500-0.89496700 C 4.45607200 5.15921200-0.81493600 H 4.91488000 6.07150400-1.18644200 C 3.10371700 5.14407100-0.51336900 H 2.47264600 6.01352800-0.62004700 C 2.54727100 3.93342400-0.05049900 S40

C 0.23033200 4.80127900 0.34097700 C -1.15943800 4.32081900 0.72153900 H -1.71076900 5.21472300 1.01967300 H -1.11142400 3.64997300 1.58663600 C -1.85497600 3.60334700-0.45379600 H -1.29170500 2.69066300-0.66976300 H -1.79021800 4.22545500-1.35526700 C 3.72250300 0.60655700-2.34373200 H 3.95479400 1.67250300-2.41114800 H 2.69721700 0.43512500-2.67404600 H 4.42034300 0.03089300-2.96285700 N -2.31776500-1.80620400 1.77550000 N -2.70520900-2.04084100-1.60064300 N -3.12103100 1.29596600-1.83696900 N -2.83883800 1.51570200 1.57089000 N 2.31899100-4.16878900 0.29302100 N 4.00472300-2.52417900 0.06848600 N 3.27152700 2.81495300 0.11925200 N 1.19382400 3.79864200 0.26668300 H 0.90498900 2.84242800 0.45550200 O 1.67129400-2.46076900 1.68863500 O 3.77913800 0.14579000-0.98425600 O 0.47321400 5.97683200 0.10572500 H 2.01837900-5.07093000-0.05111400 H -2.10578200-1.35432600-1.15973600 H -2.11280800 1.06274600 1.02749400 H -2.19197500 1.04380700-1.52342500 H -1.60567500-1.29288200 1.26740500 Cl -0.17095300 0.17936600-0.22642500 Na 2.22796700-0.61049900 0.52029100 Complex of 1 KCl E(RB3LYP): -3622.49240980 a.u. Number of negative frequencies: 0 Cartesian coordinates: Symbol X Y Z C -2.87413500-1.49035200 2.94744800 C -3.57007100-2.58902900 3.41478900 H -4.13453300-2.63751500 4.33507800 C -3.41036700-3.64342000 2.47486600 H -3.83655000-4.63391900 2.55152600 S41

C -2.62118100-3.17749800 1.44006800 C -2.14090000-3.87729000 0.17449500 C -2.85351400-3.36355400-1.07281100 C -3.81413300-3.96467300-1.86412800 H -4.24020400-4.94614400-1.71154900 C -4.14354600-3.06554500-2.91446400 H -4.86275200-3.24283300-3.70141300 C -3.38047600-1.92443100-2.75667200 C -3.30205500-0.65901100-3.60401700 C -3.91386100 0.54482600-2.89736700 C -5.08583500 1.23712300-3.13820300 H -5.81167600 1.00789100-3.90580900 C -5.16345800 2.30790500-2.20520800 H -5.96088800 3.03452400-2.13626500 C -4.03852100 2.25833700-1.40353100 C -3.60055000 3.14535600-0.24148700 C -3.80649600 2.45124700 1.10032700 C -4.74002400 2.67921800 2.09384600 H -5.52180600 3.42532900 2.07141800 C -4.49102800 1.76125800 3.15086600 H -5.04795400 1.68850600 4.07445200 C -3.40538800 0.98384300 2.79501200 C -2.67575500-0.11073900 3.56476400 C -2.42623500-5.38748500 0.30547100 H -1.94897800-5.80177000 1.19819400 H -2.05764400-5.92103800-0.57691200 H -3.49963600-5.57514500 0.38913600 C -4.07104300-0.89870900-4.91859700 H -3.64119600-1.74801200-5.45905700 H -4.01168500-0.01095300-5.55575100 H -5.12739500-1.11292900-4.73164600 C -1.82215600-0.36263900-3.97064300 H -1.19641800-0.18340400-3.09004200 H -1.76430500 0.52817100-4.60635700 H -1.39458200-1.21177500-4.51657200 C -4.45565500 4.42934300-0.26330400 H -5.51692400 4.19640800-0.14213900 H -4.32927900 4.94969800-1.21748800 H -4.16950000 5.10521800 0.54756900 C -3.21370100-0.13794300 5.00937900 H -4.28345400-0.36493600 5.03329300 S42

H -3.06197000 0.83512800 5.48648800 H -2.68955000-0.90042100 5.59412000 C -1.15881200 0.22184600 3.63677600 H -0.62917400-0.55146200 4.20567200 H -1.01101800 1.18872100 4.13229600 H -0.70587300 0.28202000 2.64148700 C -0.60361100-3.66543900-0.01776900 H -0.30945300-4.14597700-0.95949000 H -0.39742200-2.59714300-0.14241300 C 0.27200700-4.19597200 1.14552900 H -0.18402400-3.93565400 2.10378900 H 0.36240500-5.28805300 1.09650900 C 1.63848000-3.53911500 1.10910200 C 3.78599200-3.65672200-0.22153500 C 4.61307900-4.59010400-0.87385300 H 4.27667800-5.61064500-1.03316200 C 5.86581300-4.17370600-1.29685700 H 6.52718000-4.86642100-1.80929900 C 6.26776600-2.85942400-1.05063900 H 7.23956800-2.49907500-1.37037700 C 5.38024500-2.00408700-0.39291000 C 5.77774400-0.60860600-0.04733300 C 6.94534000-0.38568200 0.69505200 H 7.56228300-1.23504200 0.97471700 C 7.29596100 0.89998500 1.10005500 H 8.19818800 1.06163000 1.68230600 C 6.46155100 1.97209800 0.79354700 H 6.70236200 2.96726800 1.15587100 C 5.28286800 1.79231400 0.05219000 C 4.97795000 0.49474100-0.40534200 C 4.40205100 2.97219900-0.19984300 C 4.97096900 4.15782400-0.67190200 H 6.02820800 4.19979800-0.91070500 C 4.14399900 5.26902600-0.83880500 H 4.55122400 6.20626700-1.20809300 C 2.79459100 5.17526100-0.54259900 H 2.11823600 6.00971300-0.64867300 C 2.30128400 3.93750800-0.07938700 C -0.02721600 4.72918200 0.39596600 C -1.40915800 4.20449800 0.74768400 H -1.97421300 5.07074500 1.09809300 S43

H -1.34491600 3.48793500 1.57419200 C -2.09942600 3.54063500-0.46206700 H -1.51778800 2.65872300-0.74180300 H -2.06054600 4.21836000-1.32400900 C 3.85993900 0.74022200-2.50925900 H 4.01892400 1.82242300-2.54462200 H 2.87707200 0.50250700-2.91840500 H 4.63964000 0.23115900-3.08853900 N -2.30166600-1.86612500 1.74607300 N -2.60132500-2.12282600-1.63178200 N -3.29305800 1.17813800-1.83874300 N -3.00438000 1.41562200 1.54343400 N 2.50546700-4.08354500 0.17369500 N 4.15227400-2.39457400 0.00581300 N 3.08824000 2.85878500 0.09390400 N 0.95103700 3.74605600 0.22907600 H 0.66270700 2.77469300 0.32113000 O 1.92685700-2.57482300 1.80872600 O 3.84900600 0.25490200-1.15998500 O 0.20421100 5.92249200 0.26596100 H 2.18787800-4.93660300-0.26689500 H -1.93506400-1.44949300-1.27158300 H -2.22416100 1.03260200 1.01978700 H -2.40154600 0.89997000-1.44639700 H -1.72634400-1.26087400 1.17017100 Cl -0.35781300 0.24200000-0.23829600 K 2.31726500-0.11690400 1.01795200 Complex of 1 LiCl H 2O E(RB3LYP): -3106.57186841 a.u. Number of negative frequencies: 0 Cartesian coordinates: Symbol X Y Z C 2.90774600-1.60209300-2.85790600 C 3.72977200-2.65890600-3.20015800 H 4.37426800-2.70523000-4.06647000 C 3.57545500-3.67311600-2.21753500 H 4.08820500-4.62472700-2.19932900 C 2.66371900-3.22535700-1.28015000 C 2.15549200-3.89881400-0.01195800 C 2.81993200-3.34393100 1.24212500 S44

C 3.69267500-3.93461100 2.13611400 H 4.08506800-4.93982700 2.07158900 C 3.98209300-2.98677900 3.15616100 H 4.63368900-3.14300900 4.00413700 C 3.28079700-1.82932000 2.87583100 C 3.18565600-0.51283700 3.63727400 C 3.81362000 0.63917800 2.86282200 C 5.01737600 1.29428400 3.04003800 H 5.75602800 1.06969200 3.79669500 C 5.10827300 2.31969600 2.05945700 H 5.92943400 3.01205800 1.93809100 C 3.95988900 2.28035600 1.29157100 C 3.52239700 3.14486900 0.11229700 C 3.71628400 2.42366300-1.21586200 C 4.61638800 2.66126400-2.23754800 H 5.36578300 3.43999000-2.25480000 C 4.38595100 1.69984100-3.25917100 H 4.92651900 1.62038800-4.19181100 C 3.34470700 0.88712700-2.85372500 C 2.66224600-0.27452400-3.56604800 C 2.45544600-5.40912100-0.09655400 H 2.01601400-5.84636400-0.99810400 H 2.05646400-5.92617300 0.78262000 H 3.53243500-5.59156500-0.13303000 C 3.92662100-0.66498000 4.98054400 H 3.47795300-1.46990500 5.57155800 H 3.86348300 0.26636300 5.55144800 H 4.98386300-0.90219500 4.83028000 C 1.69773700-0.19730200 3.95104600 H 1.08932100-0.08521600 3.04697500 H 1.62271400 0.73447600 4.52334100 H 1.26244700-1.00939200 4.54488700 C 4.38582200 4.42369000 0.10565500 H 5.44510200 4.18096400-0.01281900 H 4.26393300 4.96487800 1.04871700 H 4.10400900 5.08414900-0.71914000 C 3.22395100-0.37178900-4.99871600 H 4.30348700-0.54812800-4.99600100 H 3.03366100 0.55921200-5.54163200 H 2.74365400-1.19487700-5.53689700 C 1.13837200-0.00332100-3.67740700 S45

H 0.64098600-0.82242100-4.20917000 H 0.96301200 0.92849200-4.22650800 H 0.66430100 0.09377900-2.69648900 C 0.61670300-3.69272000 0.14889100 H 0.30314000-4.18187700 1.07945000 H 0.40492900-2.62640700 0.27501500 C -0.24346200-4.21221300-1.03318100 H 0.23745500-3.94964500-1.97938500 H -0.35862600-5.30139000-0.99404000 C -1.57303800-3.50080900-0.98466800 C -3.87335200-3.73700500 0.01793100 C -4.75360600-4.68795500 0.56305100 H -4.44831900-5.72433700 0.67310700 C -6.01053800-4.26255500 0.96103100 H -6.71143700-4.96661200 1.39982200 C -6.36212100-2.92250200 0.79929600 H -7.32961200-2.55768400 1.12413600 C -5.43501400-2.04388700 0.22953100 C -5.80333100-0.62032200-0.00166700 C -7.07584400-0.32537500-0.51555200 H -7.74751900-1.14120300-0.76493100 C -7.46453600 0.98950900-0.74315000 H -8.44330900 1.20540600-1.16034700 C -6.58010300 2.02740200-0.46436800 H -6.86745200 3.05160700-0.68053800 C -5.29518600 1.78313700 0.04533400 C -4.92269800 0.44443300 0.28295200 C -4.40447800 2.95379600 0.30380400 C -4.93596700 4.09402400 0.91311400 H -5.96491600 4.10473100 1.25505700 C -4.10912800 5.20597900 1.07967400 H -4.49434200 6.10861800 1.54588400 C -2.78876400 5.15742900 0.66496800 H -2.11463600 5.99418100 0.76921700 C -2.32289600 3.95778300 0.08943300 C -0.02611400 4.76958500-0.47922400 C 1.34642500 4.24645700-0.86353400 H 1.91638300 5.11571700-1.19745300 H 1.27143400 3.54720700-1.70413400 C 2.02733800 3.55093300 0.33329900 H 1.43481400 2.66799400 0.58801300 S46

H 1.98949000 4.20957500 1.21007400 C -3.32510600 0.44222100 2.10338400 H -3.55457800 1.48630200 2.32975800 H -2.25058000 0.27549200 2.18732000 H -3.87488300-0.21763000 2.78452200 Li -2.77259900-0.93157900-0.77898800 N 2.26690100-1.96142900-1.68569200 N 2.57897500-2.06474600 1.70967400 N 3.18622000 1.24863600 1.79279900 N 2.94905300 1.34170700-1.60857800 N -2.58777000-4.17631600-0.33613700 N -4.20194700-2.45200300-0.15050400 N -3.11908300 2.89029200-0.10022200 N -0.99758700 3.78133800-0.30841400 H -0.71739400 2.81352000-0.44714700 O -1.70450900-2.35996300-1.42368000 O -3.65934900 0.12778000 0.73965800 O -0.25700100 5.95785000-0.31127700 O -2.31278500 0.63636500-1.79422200 H -2.37175800-5.12397200-0.05754400 H 1.98258200-1.38433900 1.25319700 H 2.19536500 0.94180400-1.05912800 H 2.27368200 0.98865800 1.43649500 H 1.57784100-1.38737700-1.21026500 H -1.35461600 0.56342900-1.60784100 H -2.59287000 1.41782700-1.25681700 Cl 0.21917100 0.22023800 0.18657200 Complex of 1 NaCl H 2O E(RB3LYP): -3261.32579549 a.u. Number of negative frequencies: 0 Cartesian coordinates: Symbol X Y Z C -3.05222400-1.32812500 2.80237100 C -4.11691100-2.16251900 3.08421100 H -4.79500700-2.06130700 3.91957200 C -4.15462100-3.18074600 2.09419300 H -4.87310200-3.98658200 2.03677900 C -3.11523800-2.95867900 1.21118100 C -2.70843300-3.73292200-0.03710000 C -3.26931800-3.09816400-1.30354200 S47