3D Covalent Organic Frameworks with Dual Linkages for Bifunctional Cascade Catalysis

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1 [Supporting Information] 3D Covalent Organic Frameworks with Dual Linkages for Bifunctional Cascade Catalysis Hui Li,, Qinying Pan,, Yunchao Ma, Xinyu Guan, Ming Xue, Qianrong Fang,, Yushan Yan, Valentin Valtchev, and Shilun Qiu, State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun , P. R. China Department of Chemical and Biomolecular Engineering, Center for Catalytic Science and Technology, University of Delaware, Newark, DE 19716, USA Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 Marechal Juin, Caen, France Contents: Section 1. Materials and characterization Section 2. Figures S1 28 Section 3. Tables S1 4 Section 4. References S1

2 NH2OHOHOBOBOBONNSection 1. Materials and characterization All starting materials and solvents, unless otherwise noted, were obtained from J&K scientific LTD. and used without purification. All products were isolated and handled under nitrogen using either glovebox or Schlenk line techniques. 1,3,5,7 tetraaminoadamantane (TAA) was synthesized by the method of literatures H NMR spectra were recorded on an AV400 NMR spectrometer. 13 C NMR spectra were recorded on an AVIII 500 MHz solid state NMR spectrometer. The FTIR spectra (KBr) were obtained using a SHIMADZU IRAffinity 1 Fourier transform infrared spectrophotometer. TGA was carried out under nitrogen on a SHIMADZU DTG 60 thermal analyzer at a heating rate of 10 o C min 1 to 800 o C with N 2 flow rate was 30 ml min 1. PXRD data were collected on a PANalytical B.V. Empyrean powder diffractometer using a Cu Kα source (λ = Å) over the range of 2θ = with a step size of 0.02 and 2 s per step. The sorption isotherm for N 2 was measured by using a Quantachrome Autosorb IQ analyzer with ultra high purity N 2 (99.999% purity). To estimate pore size distributions for DL COFs, nonlocal density functional theory (NLDFT) was applied to analyze the N 2 isotherm on the basis of the model of N on carbon with slit pores and the method of non negative regularization. The SEM images were obtained on JEOL JSM6700 scanning electron microscope. (1) Synthesis of model molecule with dual linkages BN+AA FPBA S2

3 NNHN2NHN2NNHN2NNNOBOBOBNHNIn this procedure, 1 adamantanamine (AA, 0.1 mmol) with 4 formylphenylboronic acid (FPBA, 0.1 mmol) were dissolved in 2 ml DMSO d 6, followed by adding a few of 4A molecular sieve. After heating at 80 o C for 2 h, the model molecule with dual linkages was obtained. 1 H NMR (400 MHz, DMSO d 6 ) δ 1.75 (m, 12 H), 2.12 (s, 3 H), 7.71 (d, 2 H), 7.82 (d, 2 H), 8.12 (s, 1 H). (2) Synthesis of DL COF 1 NH2+OBOOHFPBA NTAA NA Pyrex tube measuring o.d. i.d. = 10 8 mm 2 was charged with FPBA (30.0 mg, 0.2 mmol) and TAA (9.8 mg, 0.05 mmol) in a mixed solution of dioxane (0.5 ml) and mesitylene (0.5 ml). The tube was flash frozen at 77 K (LN 2 bath), evacuated to an internal pressure of 0.15 mmhg and flame sealed. Upon sealing the length of the tube was reduced to ca. 13 cm. The reaction mixture was heated at 120 C for 3 days to afford a white precipitate which was isolated by filtration over a medium glass frit and washed with anhydrous tetrahydrofuran (THF, 20.0 ml). The product was immersed in anhydrous THF (20.0 ml) for 8 h, during which the activation solvent was decanted and freshly replenished four times. The S3

4 solvent was removed under vacuum at 80 C to afford DL COF 1 as a white powder (26.7 mg, 82%). Anal. Calcd for C 19 H 16 B 2 N 2 O 2 : C, 70.01; H, 4.95; N, Found: C, 69.36; H, 4.92; N, (3) Synthesis of DL COF 2 NH2NNHN2NHN2NNHN2NNNF+OBBOOOFBFBHOOHNFFFPBA NTAA NNSimilar to DL COF 1, FPBA was treated with FFPBA (33.6 mg, 0.2 mmol) in a mixed solution of dioxane (0.5 ml) and mesitylene (0.5 ml). The tube was flash frozen at 77 K (LN 2 bath), evacuated to an internal pressure of 0.15 mmhg, and flame sealed. Upon sealing the length of the tube was reduced to ca. 13 cm. The reaction mixture was heated at 120 C for 3 days to afford a white precipitate which was isolated by filtration over a medium glass frit and washed with anhydrous THF (20.0 ml). The product was immersed in anhydrous THF (20.0 ml) for 8 h, during which the activation solvent was decanted and freshly replenished four times. The solvent was removed under vacuum at 80 C to afford DL COF 2 as a white powder (30.9 mg, 85%). Anal. Calcd for C 19 H 16 B 2 F 2 N 2 O 2 : C, 62.70; H, 4.43; N, Found: C, 61.21; H, 4.40; N, (3) Catalytic reactions S4

5 Typically, the catalytic reaction was performed with 1 mmol of each substrate in CDCl 3 (3 ml) with DL COF 1 or 2 (10 mol%) for 20 h at room temperature. The conversion of the reaction was detected by 1 H NMR spectroscopy as based on the starting materials. 1 H NMR (400 MHz, CDCl 3 ) for benzaldehyde: δ 7.5~7.7 (m, 3H), 7.9 (m, 2H), 10.0 (s, 1H); benzylidene malononitrile (R 1 = R 2 = CN): δ 7.5 (m, 2H), 7.6 (m, 1H), 7.8 (s, 1H), 7.9 (d, 2H); ethyl trans α cyanocinnamate (R 1 = CN and R 2 = COOC 2 H 5 ): δ 1.4 (t, 3H), 4.4 (q, 2H), 7.5~7.6 (m, 3H), 8.0 (m, 2H), 8.3 (s, 1H); 3 benzylidene 2,4 pentanedione (R 1 = R 2 = COCH 3 ): δ 2.6 (s, 6H), 7.6~7.7 (m, 3H), 8.0 (m, 2H), 8.2 (s, 1H). S5

6 Section 2. Figures S1 28 Figure S1. SEM image of DL COF 1. Figure S2. SEM image of DL COF 2. S6

7 Peak (cm 1 ) Assignment and Notes for DL COF (s) O H stretch from end B(OH) 2 or OH groups at the surface of crystallites (w) Aromatic C H stretch from phenyl group (w) Aromatic C H stretch from phenyl group (w) Alkene C H stretch from imine (w) C H stretch from TAA building block (w) C H stretch from TAA building block (s) C=N stretch from Imine (w) Aromatic ring vibration mode from phenyl group (m) Aromatic ring vibration mode from phenyl group (m) Phenyl ring C=C vibrational mode (w) Phenyl ring C=C vibrational mode (w) Phenyl ring C=C vibrational mode (w) phenyl ring C=C vibrational mode (w) phenyl ring C=C vibrational mode (S) B O stretch (S) B O stretch (w) C C=N C stretch from Imine (w) C H in plane bending from phenyl group (w) C H in plane bending from phenyl group (w) B C stretch (s) B C stretch (w) B C stretch (w) Aromatic ring stretch (w) Aromatic C H out of plane bending from phenyl group (s) C H wagging from imine (m) Out of plane deformation for B 3 O 3 unit (w) Aromatic ring bending Figure S3. FT IR spectra of DL COF 1 (black), TAA (red), and FPBA (blue). S7

8 Peak (cm 1 ) Assignment and Notes for DL COF (m) O H stretch from end B(OH) 2 or OH groups at the surface of crystallites (w) Aromatic C H stretch from phenyl group (w) Alkene C H stretch from imine (w) C H stretch from TAA building block (s) C H stretch from TAA building block (s) C=N stretch from Imine (s) Aromatic ring vibration mode from phenyl group (w) Aromatic ring vibration mode from phenyl group (w) Phenyl ring C=C vibrational mode (w) Phenyl ring C=C vibrational mode (w) Phenyl ring C=C vibrational mode (w) Phenyl ring C=C vibrational mode (m) B O stretch (m) B O stretch (w) C F stretch from phenyl group (m) C H in plane bending from phenyl group (w) B C stretch (m) Aromatic ring stretch (w) Aromatic C H out of plane bending from phenyl group (w) Aromatic C H out of plane bending from phenyl group (w) C H wagging from imine (w) Out of plane deformation for B 3 O 3 unit (w) Out of plane phenyl ring deformation for benzene (w) Aromatic ring bending Figure S4. FT IR spectra of DL COF 2 (black), TAA (red), and FFPBA (blue). S8

9 Figure S5. Solid state 13 C NMR spectra of DL COF 1. Figure S6. Solid state 13 C NMR spectra of DL COF 2. S9

10 Figure S7. TGA of DL COF 1. Figure S8. TGA of DL COF 2. S10

11 Figure S9. Calculated PXRD pattern of DL COF 1 based on the ctn net in the space group of I 43d. Figure S10. Calculated PXRD pattern of DL COF 1 based on the bor net in the space group of P23. S11

12 Figure S11. The comparison of PXRD patterns for DL COF 1: experimental (a, blue) as well as calculated based on the ctn net (b, black) and the bor net (c, red). Figure S12. Calculated PXRD pattern of DL COF 2 based on the ctn net in the space group of I 43d. S12

13 Figure S13. Calculated PXRD pattern of DL COF 2 based on the bor net in the space group of P23. Figure S14. The comparison of PXRD patterns for DL COF 2: experimental (a, blue) as well as calculated based on the ctn net (b, black) and the bor net (c, red). S13

14 Figure S15. BET plot of DL COF 1 calculated from N 2 adsorption isotherm at 77 K. Figure S16. Pore size distribution histogram of DL COF 1 calculated from N 2 adsorption isotherm at 77 K. S14

15 Figure S17. BET plot of DL COF 2 calculated from N 2 adsorption isotherm at 77 K. Figure S18. Pore size distribution histogram of DL COF 2 calculated from N 2 adsorption isotherm at 77 K. S15

16 Figure S19. Conversion (%) versus time (h) for bifunctional catalytic reactions in DL COF 1 based on entry 3. Inset: the structures of substrate, intermediate and the final product. C, green; H, gray; O, red; N, blue. Figure S20. Conversion (%) versus time (h) for bifunctional catalytic reactions in DL COF 2 based on entry 4. Inset: the structures of substrate, intermediate and the final product. C, green; H, gray; O, red; N, blue. S16

17 Figure S21. Conversion (%) versus time (h) for bifunctional catalytic reactions in DL COF 1 based on entry 5. Inset: the structures of substrate, intermediate and the final product. C, green; H, gray; O, red. Figure S22. Conversion (%) versus time (h) for bifunctional catalytic reactions in DL COF 2 based on entry 6. Inset: the structures of substrate, intermediate and the final product. C, green; H, gray; O, red. S17

18 Figure S23. PXRD of DL COF 1 before (black curve) and after (red curve) the catalytic reaction. Figure S24. PXRD of DL COF 2 before (black curve) and after (red curve) the catalytic reaction. S18

19 Figure S25. N 2 sorption isotherm of DL COF 1 after the catalytic reaction. Figure S26. N 2 sorption isotherms of DL COF 2 after the catalytic reaction. S19

20 Figure S27. The recyclability study of DL COF 1 for entry 1. Figure S28. The recyclability study of DL COF 2 for entry 2. S20

21 Section 3. Tables S1 S4 Table S1. Unit cell parameters and fractional atomic coordinates for DL COF 1 calculated based on the ctn net. Space group I 43d Calculated unit cell a = b = c = Å, α = β = γ = 90 º Measured unit cell a = b = c = Å, α = β = γ = 90 º Pawley refinement R p = 1.73%; wr p = 3.21% atoms x y z N C C B O C H H H C C C C C C H H H H H C S21

22 Table S2. Unit cell parameters and fractional atomic coordinates for DL COF 1 calculated based on the bor net. Space group P23 Calculated unit cell a = b = c = Å, α = β = γ = 90 º atom x y z B C O N C H H H C C C C C C H H H H H C C C S22

23 Table S3. Unit cell parameters and fractional atomic coordinates for DL COF 2 calculated based on the ctn net. Space group I 43d Calculated unit cell a = b = c = Å, α = β = γ = 90 º Measured unit cell a = b = c = Å, α = β = γ = 90 º Pawley refinement R p = 1.66%; wr p = 3.03% atom x y z N C C B O C H H H C C C C C C H H F H H C S23

24 Table S4. Unit cell parameters and fractional atomic coordinates for DL COF 2 calculated based on the bor net. Space group P23 Calculated unit cell a = b = c = Å, α = β = γ = 90 º atom x y z B C O N C H H H C C C C C C H H H H F C C C S24

25 Section 4. References (1) Newkome, G. R.; Nayak, A.; Behera, R. K.; Moorefield, C. N.; Baker, G. R. J. Org. Chem. 1992, 57, 358. (2) Senchyk, G. A.; Lysenko, A. B.; Boldog, I.; Rusanov, E. B.; Chernega, A. N.; Krautscheid, H.; Domasevitch, K. V. Dalton Trans. 2012, 41, (3) Fang, Q. R.; Gu, S.; Zheng, J.; Zhuang, Z. B.; Qiu, S. L.; Yan, Y. S. Angew. Chem., Int. Ed. 2014, 53, S25