Supporting Information: Self-assembled benzophenone bis-urea macrocycles facilitate selective oxidations by singlet oxygen.

Transcription

1 Supporting Information: Self-assembled benzophenone bis-urea macrocycles facilitate selective oxidations by singlet oxygen. Michael F. Geer, a Michael D. Walla, a Kyril Solntsev, b Christian A. Strassert, c Linda Shimizu* a. a Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina b School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, Georgia c Physikalisches Institut and Center for Nanotechnology (CeNTech), Universitat Münster, Heisenbergstrasse Münster, Germany. List of Figures, Tables, and Schemes: Schemes: Page: Scheme S1. Synthesis of the bis-urea benzophenone macrocycle (host 1). S4 Figures: S1. S2. S3. S4. 1 H NMR (400 MHz, CDCl 3 ) of 4,4 -bis(bromomethyl) benzophenone. S4 13 C NMR (400 MHz, CDCl 3 ) of 4,4 -bis(bromomethyl) benzophenone. S5 1 H NMR (300 MHz, CDCl 3 ) of protected bis-urea macrocycle. S5 13 C NMR (300 MHz, CDCl 3 ) of protected bis-urea macrocycle. S6 S5. S6. 1 H NMR (300 MHz, δ 6 -DMSO) of benzophenone bis-urea macrocycle (host 1). 13 C NMR (75 MHz, δ 6 -DMSO) of benzophenone bis-urea macrocycle (host 1). S6 S7 S1

2 S7. Absorption and emission spectra of benzophenone (DMSO). S7 S8. Absorption and emission spectra of macrocycle 1 (DMSO). S8 S9. Comparison of the solid-state emission spectra of host 1 and benzophenone (integrating sphere). S10. Comparison of the steady-state emission spectra of benzophenone and host 1 (TCSPC). S8 S9 S11. Phosphorescence decay of benzophenone. S9 S12. Phosphorescence decay of host 1 ( nm). S10 S13. Phosphorescence decay of host 1 (5 ns and 20 ns scale). S10 S14. Excitation spectra of host 1 and emission of singlet oxygen (in CDCl 3 ). S11 S15. TGA desorption of 2-methyl-2-butene. S12 S16. S17. 1 H-NMR (400 MHz, δ 6 -DMSO) of host 1 2-2methyl-2-butene complex. S13 1 H-NMR (400 MHz, δ 6 -DMSO) of host 1 cumene complex. S14 S18. Comparison of PXRD pattern of host 1, host 1 2-methyl-2-butene, and host 1 3-methyl-2-buten-1-ol. S16 S19. Comparison of simulated and experimental host 1 DMSO PXRD patterns. S17 S20. PXRD pattern of host 1 2-methyl-2-butene. S18 S21. PXRD pattern of host 1 3-methyl-2-buten-1-ol. S19 S22. PXRD pattern of host 1 DMSO (simulated). S20 S23. PXRD pattern of host 1 DMSO (experimental). S21 S24. PXRD pattern of host 1 empty. S22 S25. SEM image of host 1 crystals. S23 S26. GC trace of oxidation products of 2-methyl-2-butene isolated from host 1. S23 S27. Mass spectra of oxidation products of 2-methyl-2-butene isolated from host 1. S24 S28. GC trace of oxidation products of cumene isolated from host 1. S24 S29. Mass spectra of oxidation products of cumene isolated from host 1. S25 S30 Mass spectra of oxidation products of cumene isolated from host 1. S25 S2

3 S31. 1 H-NMR (400 MHz, δ 6 -DMSO) of host 1 oxydation products from 2- methyl-2-butene. S26 S32. Comparison of 1 H-NMR (300 MHz, δ 3 -AcCN) of 2-2methyl-2-butene, product isolated from oxidation of 2-methyl-2-butene and 3-methyl-2- buten-1-ol. S33. Comparison of 1 H-NMR (300 MHz, δ 3 -AcCN) of oxidation products of 2- methy-2-butene at 0, 30, 60, 120, and 180 min. S34. Comparison of GC of oxidation products from suspension of host 1 in acetonitrile. S35. Comparison of GC of oxidation products from suspension of host 1 in acetonitrile/water mixtures. S36. Comparison of EPR spectra of host 1, host 1 after exposure to fluorescent light, host 1 after exposure to UV light. S37. Comparison of EPR spectra of benzophenone, host 1 (ambient conditions), and host 1 (1 h UV exposure). S27 S28 S29 S29 S30 S31 S38. EPR spectra of host 1 cumene before and after UV irradiation. S31 S39. EPR spectra of host 1 2-methyl-2-butene before and after UV irradiation. S32 S40. Molar absorptivity of host 1 in DMSO. S32 S41. Molar absorptivity of benzophenone in DMSO. S33 S42. PXRD pattern of host 1 cumene. S33 S43. IR spectra of host 1. S34 S44. GC trace of products isolated after irradiation under argon. S35 Tables: Table S1. Time constants and pre-exponential factors of multi-exponential fitting the emission transients of solid-state host 1. S11 Table S2. Host 1:guest ratios as determined by TGA S13 Table S3. Host 1:guest ratios as determined by 1 H-NMR S15 Table S4. Percent conversion of 2-2methyl-2-butene over 30, 60 and 120 min as determined by 1 H-NMR S28 Table S5. List of IR peaks of host 1. S34 S3

4 Scheme S1. Synthesis of the bis-urea benzophenone macrocycle (host 1). Reagents and Conditions: 4,4-dimethylbenzophenone was reacted with N-bromosuccinimide (NBS) and 2,2 - azobis(isobutyronitrile) (AIBN) in CCl 4 to produce 4,4 -bis(bromomethyl) benzophenone. This was then reacted with triazinanone and NaH in refluxing THF to give the cyclized product. The protected macrocycle was deprotected in an acidic diethanol amine aqueous/methanol mixture to yield the desired bis-urea benzophenone macrocycle (1). Figure S1. 1 H NMR (300 MHz, CDCl 3 ) of 4,4 -bis(bromomethyl) benzophenone. S4

5 Figure S2. 13 C NMR (75 MHz, CDCl 3 ) of 4,4 -bis(bromomethyl) benzophenone. Figure S3. 1 H NMR (300 MHz, CDCl 3 ) of protected bis-urea macrocycle. S5

6 Figure S4. 13 C NMR (75 MHz, CDCl 3 ) of protected bis-urea macrocycle. Figure S5. 1 H NMR (300 MHz, δ 6 -DMSO) of benzophenone bis-urea macrocycle (host 1). S6

7 Absorption (O.D.) Fluorescence intensity (a.u) Figure S6. 13 C-NMR (75 MHz, δ 6 -DMSO) of benzophenone bis-urea macrocycle (host 1). Phosphorescence study of Host Absorbance spectra of benzophenone 24 Fluorescence spectra of benzophenone Concentrations: Concentrations: Wavelength (nm) Wavelength (nm) Figure S7. Absorption and emission spectra of benzophenone (DMSO). S7

8 Intensity (CPS) Intensity (CPS) Absorption (O.D.) Fluorescence intensity (a.u.) 0.10 Fluorescence spectra of host 1 in DMSO 25 Fluorescence spectra of host 1 in DMSO Concentration: Concentration: Wavelength (nm) Wavelength (nm) Figure S8. Absorption and emission spectra of macrocycle 1 (DMSO). Quantum yield solid-state study: 5x10 4 Emission spectra of host 1 crystals 3.0x10 5 Emmision spectra of solid benzophenone 4x x x10 5 3x x10 5 2x x10 5 1x x Wavelength (nm) Wavelength (nm) Figure S9. Emission spectra of host 1 and benzophenone powder samples taken in the Quata-φ integrating sphere. S8

9 Emission Intensity (counts) Emission intensity (counts) Lifetime studies: Steady-state emmision taken on time-resolved TCSPC apparatus 6x10 3 5x10 3 4x10 3 ex 372 nm host MHz benzophenone 10 KHz benzophenone 2.5 MHz 3x10 3 2x10 3 1x wavelength, nm Figure S10. Comparison of the steady-state emission spectra of benzophenone and host 1 (TCSPC) Phosphorescence decay of benzophenone ex 372 nm em 440 nm Time, ns Figure S11. Phosphorescence decay of benzophenone. S9

10 Normalized emission Relative emission Phosphorescence decay of host ex 372 nm em nm. =15 nm Time, ns Figure 12. Phosphorescence decay of host 1 ( nm). Phosphorescence decay of host 1 1 ex 372 nm em 440 nm ns full scale 20 ns full scale IRF 1E-3 1E time, ns Figure S13. Phosphorescence decay of host 1 (5 ns and 20 ns scale). S10

11 Table S1. Values of the time constants (τ i ) and normalized (to 1) pre-exponential factors (A i ) of the multi-exponential function fitting the emission transients of solid-state host 1 at room temperature. The excitation wavelength was 372 nm. Timescale τ 1, ns 1 2 τ A 2, 1 ns A 2 τ 3, ns A 3 τ 4, ns A 4 τ av, ns 20 ns ns The fit quality was inspected using the weighted residuals, and the values of 2 which in all cases was < All amplitudes are normalized in a following way: n i 1 Ai 1 Singlet oxygen photoluminescence study: Figure S14. a) The absorption spectra of host 1 crystal suspension showing a λ max of 345 nm. b) The near IR emission spectra of singlet oxygen produced from the excitation of the host 1 crystals at λ max. S11

12 Determination of guest loading: Thermogravimetric analysis (TGA): Figure S15. TGA desorption of 2-methyl-2-butene. The host 1:guest ratios were calculated using the following formula: S12

13 Table S2: Absorption of guests by host 1 as determined by TGA experiments. Alkene 2-methyl-2-butene Loading (host:guest) a 3.0:1 Guest cumene (isopropyl benzene) Loading (host:guest) a 5.6:1 2,3-dimethyl-2-butene 4.0:1 hex-5-enenitrile 5:1 3-methyl-2-buten-1-ol 4.0:1 cyclohexadiene 2:1 2-methyl-2-pentene 5.0:1 Divinyl benzene 3.5:1 trans-2-pentene 2.7:1 α-methyl styrene 3:1 4-methyl-2-pentene 6.5:1 β-methyl styrene 2.5:1 a all host:guest ratios are an average of at least 3 separate loading experiments. NMR : Figure S16. 1 H-NMR (400 MHz, δ 6 -DMSO) of host 1 2-2methyl-2-butene complex. S13

14 Figure S17. 1 H-NMR (400 MHz, δ 6 -DMSO) of host 1 cumene complex. The host 1:guest ratios were calculated using the following formulas: S14

15 Table S3: Molar ratios of host 1:guest by NMR Alkene 2-methyl-2-butene Loading (host:guest) a 3.0:1 Guest cumene (isopropyl benzene) Loading (host:guest) a 5.6:1 2,3-dimethyl-2-butene 4.5:1 hex-5-enenitrile 5.8:1 3-methyl-2-buten-1-ol 4.0:1 cyclohexadiene 2.2:1 2-methyl-2-pentene 5.2:1 Divinyl benzene 3.9:1 trans-2-pentene 2.7:1 α-methyl styrene 3.6:1 4-methyl-2-pentene 6.8:1 β-methyl styrene 2.8:1 a all host:guest ratios are an average of at least 3 separate loading experiments. S15

16 PXRD of Host 1 and inclusion complex: Figure S18. Comparison of PXRD patterns of host 1, host 1 2-methyl-2-butene, host 1 3- methyl-2-butene-1-ol, and host 1 cumene. S16

17 Figure S19. Comparison of simulated and experimental host 1 DMSO PXRD patterns. S17

18 Figure S20. PXRD pattern of host 1 2-methyl-2-butene. S18

19 Figure S21. PXRD pattern of host 1 3-methyl-2-buten-1-ol. S19

20 Figure 22. PXRD pattern of host 1 DMSO (simulated). S20

21 Figure S23. PXRD pattern of host 1 DMSO (experimental). S21

22 Figure S24. PXRD pattern of empty host 1. S22

23 Scanning electrom microscopy (SEM): SEM was taken as previously reported. 1 Freshly recrystallized assembled host 1 was loaded onto a silicon wafer The image was recorded on a Quanta 200 SEM with accelerating voltage of 30 kv. Oxidation General. Figure S25. SEM image of the host 1 crystals. Figure S26. GC trace of oxidation products of 2-methyl-2-butene isolated from host 1. S23

24 Figure S27. Mass spectra of oxidation products of 2-methyl-2-butene isolated from host 1. Figure S28. GC trace of oxidation products of cumene isolated from host 1. S24

25 Figure S29. Mass spectra of oxidation products of cumene isolated from host 1 Figure S30. Mass spectra of oxidation products of cumene isolated from host 1. S25

26 Figure S31. butene. 1 H-NMR (400 MHz, δ 6 -DMSO) of host 1 oxidation products from 2-methyl-2- S26

27 Figure S32. Comparison of 1 H-NMR (300 MHz, δ 3 -AcCN) of oxidation products of 2-methy-2- butene at 0, 30, 60, 120, and 180 min. S27

28 Figure S33. Comparison of 1 H-NMR (300 MHz, δ 3 -AcCN) of oxidation products of 2-methy-2- butene at 0, 30, 60, 120, and 180 min. The % conversion were determined by the following equations: Run time Table S4. % conversion of oxidation of 2-methyl-2-butene as determined by 1 H-NMR Integration of peak H c Integration of peak H d Integration of peak H III Integration of peak H IV Ave integration of 3- methyl-2- butene-1- ol Ave peak integration of 2- methyl-2- butene 2 h h min % conversion S28

29 Catalytic study:. Figure S34. Comparison of GC of oxidation products from suspension of host 1 in acetonitrile. Figure S35. Comparison of GC of oxidation products from suspension of host 1 in acetonitrile/water mixtures. S29

30 Relative intensity (a.u.) Intensity (a.u.) Host 1, 0 min Host 1, 30 min fluorescent light Host 1, 30 min UV light Field (g-factor) Figure S36. Comparison of EPR spectra of host 1, host 1 after exposure to fluorescent light, host 1 after exposure to UV light EPR spectra of empty host Field (g-factor) benzophenone host 1 host 1/1h UV Figure S37. Comparison of EPR spectra of benzophenone, host 1 (ambient conditions), and host 1 (1 h UV exposure). S30

31 Intensity (a.u.) relative intensity (a.u.) EPR spectra of host 1 cumene crystals host 1*cumene (amb) host 1*cumene (1hUV) Field (g-factor) Figure S38. EPR spectra of host 1 cumene before and after UV irradiation EPR of host 1 2-methyl-2-butene Field (g-factor) ambient 1 h UV Figure S39. EPR spectra of host 1 2-methyl-2-butene before and after UV irradiation. S31

32 Figure S40. Molar absorptivity of host 1 in DMSO Figure S41. Molar absorptivity of benzophenone in DMSO. S32

33 Figure S42. PXRD pattern of host 1 cumene. Figure S43. IR spectra of host 1. S33

34 Table S5. List of major peaks in the IR spectra before and after UV irradiation. Host 1 (cm -1 ) Host 1 1 h UV irradiation (cm -1 ) Figure S44. a) GC trace of isolated products from host 1 2-methyl-2-butene after irradiation under argon. b) GC trace of isolated products from host 1 cumene after irradiation under argon. References: 1. Mitchell, A. R.; Pagoria, P. F.; Coon, C. L.; Jessop, E. S.; Poco, J. F.; Tarver, C. M.; Breithaupt, R. D.; Moody, G. L., Nitroureas.1. Synthesis, Scale-up and Characterization of K-6. Propell Explos Pyrot 1994, 19 (5), S34

35 2. Dewal, M. B.; Xu, Y. W.; Yang, J.; Mohammed, F.; Smith, M. D.; Shimizu, L. S., Manipulating the cavity of a porous material changes the photoreactivity of included guests. Chem Commun 2008, (33), S35