Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 Ternary Complexes Comprising Cucurbit[10]uril, Porphyrins, and Guests Supporting Information Angew. Chem. by Simin Liu, Atindra D. Shukla, Suresh Gadde, Brian D. Wagner*, Angel E. Kaifer, and Lyle Isaacs* Department of Chemistry and Biochemistry, University of Maryland College Park, MD 20742, USA; Department of Chemistry, University of Prince Edward Island, Charlottetown, Prince Edward Island, Canada C1A 4P3; Center for Supramolecular Science and Department of Chemistry, University of Miami, Coral Gables, FL 33124, USA Table of Contents Pages Table of Contents. S1 General Experimental Section. S2 UV/Vis spectra for 1 4 and CB[10] 1 CB[10] 4. S3 S4 Fluorescence spectra and lifetimes for 2 and CB[10] 2. S5 S6 Electrochemical measurements for 3, CB[10] 3, 4, and CB[10] 4. S7 S10 ES-MS spectra for CB[10] 1 CB[10] 4. S11 S14 1 H NMR dilution experiments for CB[10] 1 and CB[10] 2. S15 S16 1 H NMR exchange reaction kinetics for CB[10] 2 and CB[5]. S17 1 H NMR titration of CB[10] 2 with pyridine. S18 S19 UV/Vis titration of CB[10] 2 with pyridine. S20 UV/Vis titration data for CB[10] 2 with 2-picoline and 3-picoline. S21 S22 Analysis of 1 H NMR titration data for CB[10] 2 with 4-picoline and 4-methoxypyridine. S23 1 H NMR spectra for CB[10] 2 in the presence of various guests. S24 S32 UV/Vis and 1 H NMR spectra for CB[10] 2 with isoquinoline. S33 S35 UV/Vis and 1 H NMR spectra for CB[10] 2 with quinoline. S36 S37 1 H NMR spectra for CB[10] 2 with 4,4 -bipyridine. S38 1 H NMR spectra for CB[10] 1 with pyridine. S39 S1

3 General Experimental Section. CB[10] was prepared by the literature procedures. [1] The guests used in this study were prepared by the literature procedures or purchased from commercial suppliers and were used without further purification. Melting points were measured on a Meltemp apparatus in open capillary tubes and are uncorrected. IR spectra were recorded on commercial spectrophotometers as KBr pellets and are reported in cm -1. NMR spectra were measured on spectrometers operating at 400 or 500 MHz for 1 H and 100 or 125 MHz for 13 C. Mass spectrometry was performed using a VG 7070E magnetic sector instrument by fast atom bombardment (FAB) using the indicated matrix or on a JEOL AccuTOF electrospray instrument. Fluorescence spectra were measured on a Photon Technologies International LS-100 luminescence spectrometer, with excitation and emission monochrometer bandpasses set at 3 nm and an excitation wavelength of 420 nm. Time-resolved fluorescence was measured on the same solutions using a Photon Technologies International Timemaster fluorescence lifetime spectrometer, with excitation at 380 nm (for increased excitation lamp intensity as compared to 420 nm as used for the steady-state measurements) and emission measured at 630 nm. This instrument measures fluorescence decay curves using the stroboscopic technique; [3] resulting decay curves were well fit to one-exponential decay functions using supplied deconvolution software, with excellent χ 2 fit parameters (typically in the range of 0.90 to 1.2). Purging the solutions with Ar to remove O 2 was found to have no measurable effect on either steady-state fluorescence intensities or fluorescence lifetimes. Voltammetric experiments were recorded with a BAS 100B/W electrochemical workstation, using a single-compartment glass cell fitted with a working glassy carbon electrode (0.071cm 2 ), a Pt auxiliary electrode and a Ag/AgCl reference electrode. All solutions were purged with purified nitrogen to remove residual oxygen before the experiments. The working electrode was polished with a 0.05-µm alumina/water slurry on a felt surface. Computational results were obtained using Spartan 02 running on a Macintosh personal computer. UV/Vis titrations were performed on a Cary 100 UV/Vis instrument with 1 cm pathlength cells at 298K and analyzed using Associate v [2] References: [1] S. Liu, P. Y. Zavalij, L. Isaacs, J. Am. Chem. Soc. 2005, 127, A. I. Day, R. J. Blanch, A. P. Arnold, S. Lorenzo, G. R. Lewis, I. Dance, Angew. Chem., Int. Ed. 2002, 41, [2] B. R. Peterson, Ph.D. Thesis, University of California, Los Angeles, [3] W. R Ware, D. R. James, A. Siemiarczuk, Rev. Sci. Instrum. 1992, 63, S2

4 Figure S1. UV/Vis spectra recorded (pd 7.4 sodium phosphate buffered D 2 O, RT) for: a) 1 and CB[10] 1, b) 2 and CB[10] 2. S3

5 Figure S2. UV/Vis spectra recorded (pd 7.4 sodium phosphate buffered D 2 O, RT) for: a) 3 and CB[10] 3, b) 4 and CB[10] 4. S4

6 15 Fluorescence Intensity / 10 4 cps Wavelength / nm Figure S3. Fluorescence spectra recorded for 2 (5.4 µm, red) and CB[10] 2 (4.6 µm, blue) with an excitation wavelength of 420 nm. S5

7 Figure S4. Fluorescence lifetime measurements for free 2 and CB[10] 2. S6

8 Figure S5. Electrochemical measurements recorded for 3 (top) and CB[10] 3 (bottom) in 100 mm sodium phosphate buffer (ph 7.4) with different scan rates. S7

9 Figure S6. Comparison of the CVs for 3 and CB[10] 3 with a scan rate of 100 mv / s. Figure S7. Square wave voltammetry showing the Fe(III)/Fe(II) reduction for 3 (blue) and CB[10] 3 (black). S8

10 Figure S8. Electrochemical measurements recorded for 4 (top) and CB[10] 4 (bottom) in 100 mm sodium phosphate buffer (ph 7.4) with different scan rates. S9

11 Figure S9. Comparison of the CVs for 4 and CB[10] 4 with a scan rate of 100 mv / s. Figure S10. Square wave voltammetry showing the Fe(III)/Fe(II) reduction for 4 (blue) and CB[10] 4 (black). S10

12 Figure S11. ES-MS spectrum recorded for CB[10] 1. S11

13 Figure S12. ES-MS spectrum recorded for CB[10] 2. S12

14 Figure S13. ES-MS spectrum recorded for CB[10] 3. S13

15 Figure S14. ES-MS spectrum recorded for CB[10] 4. S14

16 Figure S15. 1 H NMR spectra recorded (500 MHz, RT, pd mm sodium phosphate buffered D 2 O) for CB[10] 1 from 1.0 mm to 0.01 mm. S15

17 Figure S16. 1 H NMR spectra recorded (500 MHz, RT, pd mm sodium phosphate buffered D 2 O) for CB[10] 2 from 1.0 mm to 0.01 mm. S16

18 Figure S17. 1 H NMR spectra recorded (500 MHz, RT, pd mm sodium phosphate buffered D 2 O) for CB[10] 2, 1 minute after addition of 0.5 eq. CB[5] and 1 minute after addition of 1.3 eq. CB[5]. S17

19 Figure S18. 1 H NMR spectra recorded (500 MHz, RT, pd mm sodium phosphate buffered D 2 O) for CB[10] 2 during the titration with pyridine. S18

20 Figure S19. 1 H NMR spectra recorded (400 MHz, RT, pd mm sodium phosphate buffered D 2 O) for pyridine, a 1:1 mixture of pyridine and 2, and a 1:1 mixture of pyridine and 1. S19

21 Figure S20. Top: UV/Vis spectra recorded during the titration of CB[10] 2 (35.3 µm) with pyridine (5) (0 to 679 µm). Bottom: curve fitting using Associate 1.6 to determine K a = 6650 ± 700 M -1. S20

22 Figure S21. Top: UV/Vis spectra recorded during the titration of CB[10] 2 (30 µm) with 2- picoline (0 to 161 µm). Bottom: curve fitting using Associate 1.6 to determine K a = ± M -1. S21

23 Figure S22. Top: UV/Vis spectra recorded during the titration of CB[10] 2 (29 µm) with 3- picoline (0 to 161 µm). Bottom: curve fitting using Associate 1.6 to determine K a = ± M -1. S22

24 Figure S23. Associate 1.6 fitting of the data obtained from a titration of CB[10] 2 (50 µm) with 4-methoxypyridine (0 to 344 µm) to yield K a = ± 600 M -1. Figure S24. Associate 1.6 fitting of the data obtained from a titration of CB[10] 2 (50 µm) with 4-picoline (0 to 312 µm) to yield K a = ± 3500 M -1. S23

25 Figure S25. 1 H NMR spectra recorded for CB[10] 2 and benzene (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S24

26 Figure S26. 1 H NMR spectra recorded for CB[10] 2 and toluene (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S25

27 Figure S27. 1 H NMR spectra recorded for CB[10] 2 and ethylbenzene (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S26

28 Figure S28. 1 H NMR spectra recorded for CB[10] 2 and furan (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S27

29 Figure S29. 1 H NMR spectra recorded for CB[10] 2 and pyrrole (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S28

30 Figure S30. 1 H NMR spectra recorded for CB[10] 2 and pyrrolidine (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S29

31 Figure S31. 1 H NMR spectra recorded for CB[10] 2 and imidazole (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S30

32 Figure S32. 1 H NMR spectra recorded for CB[10] 2 and 2,6-lutidine (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S31

33 Figure S33. 1 H NMR spectra recorded for CB[10] 2 and p-toluenesulfonic acid (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S32

34 Expansions Figure S34. UV/Vis spectra recorded for CB[10] 2 (10 µm, 25 mm sodium phosphate buffer, pd 7.4, RT) during titration with isoquinoline (0 74 µm). Two successive isosbestic points (1 st isosbestic point, blue arrows; 2 nd isosbestic point, red arrows) are noted during this titration. This observation is consistent with the formation of ternary (e.g. CB[10] 2 isoquinoline) and quaternary (CB[10] 2 isoquinoline 2 ) complexes. Alternatively, this observation could reflect conformational heterogeneity in this system. Unfortunately, we have not been able to elucidate the geometrical details of these complexes because they do not exhibit slow exchange kinetics on the chemical shift timescale above 1:0.5 stoichiometry (see Figure S35 and S36). S33

35 Figure S35. 1 H NMR spectra recorded for CB[10] 2 and isoquinoline (500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT). S34

36 Figure S36. 1 H NMR spectra recorded for CB[10] 2 (1 mm, 500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT) during the titration with isoquinoline (0 6 mm). S35

37 Figure S37. UV/Vis spectra recorded for CB[10] 2 (30 µm, 25 mm sodium phosphate buffer, pd 7.4, RT) during titration with quinoline (0 193 µm). Two successive isosbestic points (1 st isosbestic point, blue arrows; 2 nd isosbestic point, red arrows) are noted during this titration. This observation is consistent with the formation of ternary (e.g. CB[10] 2 quinoline) and quaternary (CB[10] 2 quinoline) complexes. Alternatively, this observation could reflect conformational heterogeneity in this system. Unfortunately, we have not been able to elucidate the geometrical details of these complexes because they do not exhibit slow exchange kinetics on the chemical shift timescale above 1:0.5 stoichiometry (see Figure S38). S36

38 Figure S38. 1 H NMR spectra recorded for CB[10] 2 (1 mm, 500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT) during the titration with quinoline (0 4 mm). S37

39 Figure S39. 1 H NMR spectra recorded for CB[10] 2 (0.1 mm, 500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT) during the titration with 4,4 -bipyridine (0 0.2 mm). S38

40 Figure S40. 1 H NMR spectra recorded for CB[10] 1 (0.1 mm, 500 MHz, 25 mm sodium phosphate buffered D 2 O, pd 7.4, RT) during the titration with pyridine ( mm). S39