Supporting Information. for

Transcription

1 Supporting Information for Hybrid Triazine-Boron 2D Covalent Organic Frameworks Synthesis, Characterization and DFT Approach to Layer Interaction Energies Krzysztof Gontarczyk, [a] Wojciech Bury, [a,b] Janusz Serwatowski, [a] Piotr Wieciński, [a] Krzysztof Woźniak, [c] Krzysztof Durka, [a] * Sergiusz Luliński [a] * [a] Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, Warszawa, Poland [b] Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wrocław, Poland [c] University of Warsaw, Biological and Chemical Research Centre, Żwirki i Wigury Warszawa, Poland Corresponding authors kdurka@gmail.com; serek@ch.pw.edu.pl S-1

2 Table of Contents 1. FTIR (ATR) spectra of BTA-COF1-4..S-3 2. PXRD analysis of BTA-COF S-5 3. TGA curves of BTA-COF1-4 S-7 4. N 2 sorption analysis of BTA-COF S-9 5. SEM analysis of BTA-COF1-4 S Computational modeling.s H NMR spectra of hydrolyzed BTA-COF1-4 samples..s H and 13 C NMR spectra of BTA-COF precursors..... S-26 S-2

3 1. FTIR (ATR) spectra of BTA-COF1-4 Figure S1. IR spectrum of BTA-COF1. Figure S2. IR spectrum of BTA-COF2. S-3

4 Figure S3. IR spectrum of BTA-COF3. Figure S4. IR spectrum of BTA-COF4. S-4

5 2. PXRD analysis of BTA-COF1-4. Figure S5. PXRD pattern of BTA-COF1. Figure S6. PXRD pattern of BTA-COF2. S-5

6 Figure S7. PXRD pattern of BTA-COF3. Figure S8. PXRD pattern of BTA-COF4. S-6

7 NLDFT pore size distribution Differential pore volume [cc/gå] BTA-COF-1 BTA-COF-2 BTA-COF-3 BTA-COF pore width [Å] Figure S9. NLDFT pore size distribution for BTA-COF-1-4. S-7

8 3. TGA curves of BTA-COF1-4 Figure S10. TGA curve for BTA-COF1. Figure S11. TGA curve for BTA-COF2. S-8

9 Figure S12. TGA curve for BTA-COF3. Figure S13. TGA curve for BTA-COF4. S-9

10 4. N 2 sorption analysis of BTA-COF1-4. Figure S14. N 2 sorption isotherm of BTA COF 1. S-10

11 Figure S15. N 2 sorption isotherm of BTA COF 2. S-11

12 Figure S16. N 2 sorption isotherm of BTA COF 3. S-12

13 Figure S17. N 2 sorption isotherm of BTA-COF 4. S-13

14 5. SEM analysis of BTA-COF1-4. Figure S18. Selected SEM pictures of BTA-COF1. S-14

15 Figure S19. Selected SEM pictures of BTA-COF2. S-15

16 Figure S20. Selected SEM pictures of BTA-COF3. S-16

17 Figure S21. Selected SEM pictures of BTA-COF4. S-17

18 6. Computational modeling Table S1. Fractional atomic coordinates for eclipsed model of BTA-COF1 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 3.27 Å V = 1398 Å 3 Symmetry: P-6m2 x y z O N C C C C C C C C B H H H Table S2. Fractional atomic coordinates for eclipsed model of BTA-COF2 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 3.41 Å V = 5812 Å 3 Symmetry: P6/mmm x y z O N C C C C C C C C C C B H H H H H S-18

19 Table S3. Fractional atomic coordinates for eclipsed model of BTA-COF3 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 3.41 Å V = 5835 Å 3 Symmetry: P6/mmm x y z O N C C C C C C C C C B H H H H H H C C Table S4. Fractional atomic coordinates for eclipsed AA_I model of BTA-COF4 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 3.28 Å V = 614 Å 3 Symmetry: P3m x y z B C O N C C C C H H Table S5. Fractional atomic coordinates for eclipsed AA_II model of BTA-COF4 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 6.53 Å V = 1228 Å 3 Symmetry: P-3m x y z O S-19

20 N C C C C C B H H Table S6. Fractional atomic coordinates for staggered AB_I model of BTA-COF4 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 5.80 Å V = 1092 Å 3 Symmetry: P3m x y z B C O N C C C C H H B C O N C C C C H H Table S7. Fractional atomic coordinates for staggered AB_II model of BTA-COF4 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 5.88 Å V = 1103 Å 3 Symmetry: P-3m x y z C B N O C C C C S-20

21 H H Table S8. Fractional atomic coordinates for staggered AB_III model of BTA-COF4 derived from CRYSTAL09 optimized structures. Cell parameters: a = Å c = 5.84 Å V = Å 3 Symmetry: P3m x y z O O N N C C C C C C C C C C B B H H H H Table S9. Fractional atomic coordinates for eclipsed AA model of COF-1 structure derived from CRYSTAL09 optimization. Cell parameters: a = Å c = 6.54 Å V = 1277 Å 3 Symmetry: P3m x y z B B O O C C C C H H B B O O C S-21

22 C C C H H Table S10. Fractional atomic coordinates for staggered AB model of COF-1 structure derived from CRYSTAL09 optimization. Cell parameters: a = Å c = 2.80 Å V = 1095 Å 3 Symmetry: P 63/mmc x y z B B O O C C C C H H Table S11. Fractional atomic coordinates for eclipsed AA model of CTF-1 structure derived from CRYSTAL09 optimization. Cell parameters: a = Å c = 6.57 Å V = Å 3 Symmetry: P3m x y z C C N N C C C C H H C C N N C C C C H H S-22

23 Table S12. Fractional atomic coordinates for eclipsed AB model of CTF-1 structure derived from CRYSTAL09 optimization. Cell parameters: a = Å c = 5.87 Å V = 1060 Å 3 Symmetry: P 63/mmc x y z C C N N C C C C H H S-23

24 7. 1 H NMR spectra of hydrolyzed samples of BTA-COF2-3. Figure S22. 1 H NMR (DMSO/D 2 O) spectra (aromatic region) of hydrolyzed BTA-COF2 samples dried in vacuo at the given temperature prior to analysis. S-24

25 Figure S23. 1 H NMR (DMSO/D 2 O) spectra (aromatic region) of hydrolyzed BTA-COF3 samples dried in vacuo at the given temperature prior to analysis. S-25

26 8. NMR spectra of BTA-COF precursors. Figure S24. 1 H NMR spectrum (300 MHz, DMSO) of 2,4,6-tris(4 -dihydroxyborylphenyl)- 1,3,5-triazine 2. HO OH B N N HO B OH N OH B OH Figure S C NMR spectrum of (75 MHz, DMSO) 2,4,6-tris(4 -dihydroxyborylphenyl)- 1,3,5-triazine 2. S-26

27 Figure S26. 1 H NMR spectrum of (400 MHz, DMSO) of 2,3,6,7-tetrahydroxy-9,10- dimethylanthracene (THDMA). Figure S C NMR spectrum (100 MHz, DMSO) of 2,3,6,7-tetrahydroxy-9,10- dimethylanthracene (THDMA). S-27

28 HO HO OH OH Figure S28. 1 H NMR spectrum of (400 MHz, DMSO) of 2,3,6,7-tetrahydroxy-9,10- diethylanthracene (THDEA). HO HO OH OH Figure S C NMR spectrum (100 MHz, DMSO) of 2,3,6,7-tetrahydroxy-9,10- diethylanthracene (THDEA). S-28