The Recognition of Viologen Derivatives in Water by N-Alkyl Ammonium Resorcinarene Chlorides

Transcription

1 The Recognition of Viologen Derivatives in Water by N-Alkyl Ammonium Resorcinarene Chlorides Ngong Kodiah Beyeh, a* Hyun Hwa Jo, b Igor Kolesnichenko, b Fangfang Pan, c Elina Kalenius, d Eric V. Anslyn, b* Robin H. A. Ras, a Kari Rissanen d* a Aalto University, School of Science, Department of Applied Physics, Puumiehenkuja 2, FI Espoo, Finland b The University of Texas at Austin, Department of Chemistry, Austin, Texas 78712, USA c Central China Normal University, College of Chemistry, Key Laboratory for Pesticides and Chemical Biology,152 Luoyu Road, Wuhan, Hubei , China d University of Jyvaskyla, Department of Chemistry, Nanoscience Centre, P.O. Box. 35, FI University of Jyvaskyla, Finland Supporting Information Table of Contents I Synthetic Schemes and NMR Spectra...2 II Single Crystal X-Ray Diffraction Analyses III Mass Spectrometry (MS) IV NMR Spectroscopy V Isothermal Titration Calorimetry (ITC) VI Fluorescence Spectroscopy VII References S1

2 I Synthetic Schemes and NMR Spectra Synthetic scheme and NMR spectra of compound 5. Scheme S1. Synthesis of compound 5. Figure S1. 1 H and 13 C NMR spectra of N-ethanol ammonium resorcinarene chloride 5 in CD 3 OD at 298 K. S2

3 Synthetic scheme and NMR spectra of compounds 6 and 7. Scheme S2. Synthesis of compound 6 and 7. Figure S2. 1 H and 13 C NMR spectra of N-cyclohexyl tetrabenzoxazine 6 in [D6]-DMSO at 298 K. S3

4 Figure S3. 1 H and 13 C NMR spectra of N-cyclohexyl ammonium resorcinarene chloride 7 in D 2 O at 298 K. S4

5 Synthetic scheme and NMR spectra of compounds 8 and 9. Scheme S3. Synthesis of compound 8 and 9. Figure S4. 1 H and 13 C NMR spectra of N-cyclohexyl tetrabenzoxazine 8 in [D 6 ]-DMSO at 298 K. S5

6 Figure S5. 1 H and 13 C NMR spectra of N-benzyl ammonium resorcinarene chloride 9 in [D6]-DMSO at 303 K. S6

7 Synthesis of N-methyl-4,4 -bipyridinium iodide (11). 1 Scheme S4. Synthesis of guest g (84 mmol) of 4,4 -bipyridyl were dissolved in 200 ml of DCM. 6.5 ml (105 mmol) of methyl iodide were added and the solution was refluxed overnight, producing a yellow precipitate. The solid was filtered out and dried under reduced pressure to yield g (91 %) of 11. A 1 H-NMR spectrum was obtained in D2O. Figure S6. 1 H NMR spectrum of guest 11 in D 2 O at 298 K. Synthetic scheme and NMR spectra of compounds 12 Scheme S5. Synthesis of guest 12. S7

8 Figure S7. NMR spectra of guest 12. Top: 1 H NMR in D 2 O at 298 K; middle and bottom: 1 H and 13 C NMR in [D6]-DMSO at 298 K. S8

9 Synthetic scheme and NMR spectra of compounds 13 Scheme S6. Synthesis of guest 13. Figure S8. NMR spectra of guest 13. Top: 1 H NMR in D 2 O at 298 K; middle and bottom: 1 H and 13 C NMR in [D6]-DMSO at 298 K. S9

10 II Single Crystal X-Ray Diffraction Analyses The data for crystals of 11, 11b, and 13 were collected at 123 K for 11b with an Agilent Super- Nova diffractometer using mirror-monochromatized Cu-Kα (λ= å) radiation, and at 100 K for 11 and 13 with the same diffractometer using mirror-monochromatized Mo-Kα (λ= å) radiation. CrysAlisPro 2 was used for both data collection and processing. The intensities were corrected for absorption using analytical face index absorption correction method 3 for all the three data. The structures were solved by Direct method with SHELXS 4 and refined by full-matrix least-squares methods using the OLEX2, 5 which utilizes the SHELXL-2013 module. 6 All non-hydrogen atoms in the three structures were refined with anisotropic thermal parameters. The hydrogen atoms were included in calculated positions as riding atoms, with SHELXL-2013 defaults. For 13 in the trihalide anion, one of the three halogen atoms is disordered with around 70% iodine and 30% chlorine. Their positions and ADP were constrained to the same. Crystal data 11: mm, C11H11N2I, M = , orthorhombic, space group Pbca, a = (2) Å, b = (9) Å, c = (3) Ǻ, α = 90, β = 90, γ = 90, V = (6) Ǻ 3, Z = 8, ρ = g cm 3, μ = mm 1, F(000) = 1152, reflections (θmax = ) measured (3089 unique, Rint = , completeness = 99.8%), Final R indices (I > 2σ(I)): R1= wr2 = , R indices (all data): R1= , wr2 = GOF = for 128 parameters and 0 restraints, largest diff. peak and hole 0.886/ eǻ 3. CCDC contains the supplementary data for this structure. Crystal data 11b: mm, C66H69N12I15, M = , triclinic, space group P-1, a = (3) Å, b = (8) Å, c = (10) Ǻ, α = (4), β = (3), γ = (3), V = (3) Ǻ 3, Z = 2, ρ = g cm 3, μ = mm 1, F(000) = 2688, reflections (θmax = ) measured (16350 unique, Rint = , completeness = 98.64%), Final R indices (I > 2σ(I)): R1= , wr2 = , R indices (all data): R1= , wr2 = GOF = for 844 parameters and 0 restraints, largest diff. peak and hole 1.054/ eǻ 3. CCDC contains the supplementary data for this structure. Crystal data 13: mm, C14H16N2I2.62Cl0.3, M = , triclinic, space group P-1, a = (9) Å, b = (6) Å, c = (13) Ǻ, α = (7), β = (9), γ = (7), V = (16) Ǻ 3, Z = 2, ρ = g cm 3, μ = mm 1, F(000) = 532, 6561 reflections (θmax = ) measured (5437 unique, Rint = , completeness = 99.7%), Final R indices (I > 2σ(I)): R1= , wr2 = , R indices (all data): R1= , wr2 = GOF = for 186 parameters and 0 restraints, largest diff. peak and hole 1.737/ eǻ 3. CCDC contains the supplementary data for this structure. S10

11 Figure S9. The ORTEP projection of structure 11 showing 50% probability ellipsoid S11

12 Figure S10. The ORTEP projection of structure 11b showing 50% probability ellipsoid S12

13 Figure S11. The ORTEP projection of structure 13 showing 50% probability ellipsoid III Mass Spectrometry (MS) Experimental Mass spectrometry experiments were performed with ABSciex QSTAR Elite ESI-Q-TOF mass spectrometer, equipped with an API 200 TurboIonSpray ESI source from AB Sciex. Nitrogen was used as drying and nebulization gas. The parameters were optimized to get the maximum abundance of ions under study. The measurements and data handling was done with Analyst QS 2.0 software. The ions were characterized according to comparison of theoretical and experimental m/z values and isotopic patterns calculated on basis of natural abundances of elements. Samples were prepared using HPLC solvents. For guest 12, 1 mg/ml stock solution was first prepared in H2O. The samples were further diluted (10μl/ml) either in H2O or in D2O to induce H/D-exchange. The proceeding of H/D-exchange was checked at t=15min, t=1h and t=2h, but no changes were observed as compared to first mass spectrum at t=15min. The samples were S13

14 injected into the ESI source with 5 µl/min flow rate and spectra were externally calibrated by ESI tuning mix from Agilent Technologies. In CID experiments, the ions were isolated and activated in quadrupole. Nitrogen was used as a collision gas with 5 bar pressure. The dissociation was followed as a function of CE value. Results Structures and lability of CH2 hydrogens was studied by using combination of collision induced dissociation (CID) and solution H/D exchange. In Figures S12 and S13 are presented the mass spectrometric data and plausible dissociation pathways for guest In an ESI-MS spectrum of 12 in H2O, corresponding ion 12 + was observed as a base peak at m/z 213. This ion dissociated in a CID experiment mainly by elimination of acetyl radical (C2H3O, 43 u). The identities of neutral fragments were verified by comparing the experimental and theoretical molecular weights for the fragments. Elimination of acetyl radical can be considered to take place from either one of the keto tautomers (Figure S10), but not from the enol. Keto tautomers are often more stable and in here, the stability of the keto form might be even increased due to two resonance forms. It should be noted that, generally, even electron cations (EE + ) do not produce radicals and radical cations (OE + ) as dissociation products. In here, formation of a radical cation as a major dissociation product likely results from electrochemical properties of viologen. In addition, minor dissociation route, which involves elimination of C3H4O through proton transfer to pyridine nitrogen and production of bipyridine as a fragment ion. This route could be initiated also from enol tautomer. In H/D-exchange experiment in solution, 12 + was observed to change two hydrogens to deuterium and peak at m/z 215 appeared as a base peak of the spectrum (see Figure S13). When this 12 D2 + ion was fragmented by CID, similar major and minor pathways were observed. The major pathway proceeds through elimination of 43 u, corresponding to undeuterated acetyl radical. This elimination can only occur from 12 + keto tautomer deuterated at CH2 group. This evidently confirms the lability of CH2 hydrogens and confirms the interpretation of 1 H NMR spectra. Elimination of C3H2D2O is also observed as a side pathway producing formation of bipyridine as a fragment ion. H/D-exchange was not observed when DMSO -d6 was used as a solvent (Figure S14). S14

15 Figure S12. ESI-MS analysis of 12 + in H 2 O. ESI-MS profile spectrum of 12 + in H 2 O (a), CID spectrum from isolated ion m/z 213 ([12] + ) at CE value 29 (b) and dissociation pathway of 12 + in a CID experiment (c). Major pathway marked with black and minor with grey. S15

16 Figure S13. ESI-MS analysis of 12 + in D 2 O. (a) ESI-MS profile spectrum of 12 + in D 2 O, (b) CID spectrum from isolated ion m/z 215 ([12D2] + ) at CE value 29, and (c) dissociation pathway of 12D2 + in a CID experiment. Major pathway marked with black and minor with grey. Figure S14. ESI-MS profile spectrum of 12 + in DMSO-d 6 /MeCN (1:1 v/v). No H/D-exchange observed. Measurements were not successful in 100% DMSO due to suppression of analyte signal by stable ions formed from DMSO (i.e. DMSO dimer). S16

17 IV NMR Spectroscopy For sample preparation, 5 mm stock solutions of the hosts 5, 7 and 9, and the guests were prepared in D2O. For the pure hosts and guests, 250 µl of the stock solution was measured to NMR tube and diluted with 250 µl of pure solvent to give a 2.5 mm sample concentration. For a 1:1 host-guest mixtures, 250 µl of the host and 250 µl of the guests were measured to give a 2.5 mm concentration of both the host and the guests. The spectra were calibrated using D2O signal as internal standard. Figure S15. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 11 to the host 5. Dotted lines gives an indication of the complexation induced shift changes. Figure S16. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 11 to the host 7. Dotted lines gives an indication of the complexation induced shift changes. S17

18 Figure S17. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 11 to the host 9. Dotted lines gives an indication of the complexation induced shift changes. Figure S18. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 12 to the host 5. Dotted lines gives an indication of the complexation induced shift changes. Figure S19. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 12 to the host 7. Dotted lines gives an indication of the complexation induced shift changes. S18

19 Figure S20. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 12 to the host 9. Dotted lines gives an indication of the complexation induced shift changes. Figure S21. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 13 to the host 5. Dotted lines gives an indication of the complexation induced shift changes. Figure S22. Selected region of the 1 H NMR (400 MHz, D 2 O, 298 K) spectra observed upon the addition of the guest 13 to the host 9. Dotted lines gives an indication of the complexation induced shift changes. S19

20 V Isothermal Titration Calorimetry (ITC) VP-ITC instrument made by MicroCal were used to determine the molar enthalpy ( H) of complexation. Subsequent fitting of the data to a 1:1 binding model using Origin software provides binding constant (K) and the entropy ( S). The ITC experiment was carried out by filling the sample cell with host solution, filling the syringe with the guest solution, and titrating via computer-automated injector at 298K. Blank titrations into plain solvent were also performed and subtracted from the corresponding titration to remove any effect from the heats of dilution from the titrant. Enthalpies of dilution of the hosts and the guests were determined in separate experiments, being negligible. Figure S23. ITC traces of the titration of guests (10 mm) into host 5 (1 mm) in H 2 O at 298 K. (a) guest 11, (b) guest 12, (c) guest 13. All data were fitted into a one site-model. Figure S24. ITC traces of the titration of guests (10 mm) into host 9 (1 mm)in H 2 O at 298 K. (a) guest 11, (b) guest 12, (c) guest 13. All data were fitted into a one site-model. S20

21 VI Fluorescence Spectroscopy Fluorescence spectra were recorded on a PTI QuantaMasterTM 40 intensity based spectrofluorometer equipped with 814 photomultiplier detection system (V=1000 volts). A 75 W Xenon arc lamp was used as the excitation source. The three adjustable slits before the excitation monochromator, sample compartment, and emission monochromator were set at 15 nm. The adjustable slit before the detection system was set at 10 nm. All additions of viologen guests to hosts were performed under aerobic conditions. Concentration of host: 125 µm = M Concentration of guest: 100 mm = 0.1 M Figure S25. Fluorescence changes of guest 11 (0.1 M) when titrated to host 5 (125 µm, 2 ml) in H 2 O at 298 K. Total of 4 additions of guest 11 (0.4, 1.0, 2.0, 8.0 equiv.) were added to host 5. Figure S26. Fluorescence changes of guest 12 (0.1 M) when titrated to host 5 (125 µm, 2 ml) in H 2 O at 298 K. Total of 4 additions of guest 12 (0.4, 1.0, 2.0, 8.0 equiv.) were added to host 5. S21

22 Figure S27. Fluorescence changes of guest 13 (0.1 M) when titrated to host 5 (125 µm, 2 ml) in H 2 O at 298 K. Total of 4 additions of guest 13 (0.4, 1.0, 2.0, 8.0 equiv.) were added to host 5. Figure S28. Fluorescence changes of guest 11 (0.1 M) when titrated to host 7 (125 µm, 2 ml) in H 2 O at 298 K. Total of 4 additions of guest 11 (0.4, 1.0, 2.0, 8.0 equiv.) were added to host 7. Figure S29. Fluorescence changes of guest 12 (0.1 M) when titrated to host 7 (125 µm, 2 ml) in H 2 O at 298 K. Total of 4 additions of guest 12 (0.4, 1.0, 2.0, 8.0 equiv.) were added to host 7. S22

23 VII References 1 Park, Y. S., Lee, E. J., Chun, Y. S., Yoon, Y. D., Yoon, K. B., J. Am. Chem. Soc., 2002, 124, CrysAlisPro 2013, v ; Agilent Technologies, Ltd, Yarton, UK. 3 R. C. Clark, J. S. Reid, Acta Crystallogr. Sect. A 1995, 51, G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J. Appl. Crystallogr. 2009, 42, G. M. Sheldrick, Acta Crystallogr. Sect. C 2015, 71, 3. S23