Supporting Online Material for

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1 Supporting Online Material for Porous, Crystalline, Covalent Organic Frameworks Adrien P. Côté, Annabelle I. Benin, Nathan W. Ockwig, Michael O Keeffe, Adam J. Matzger, Omar M. Yaghi* *To whom correspondence should be addressed. oyaghi@umich.edu This PDF file includes: Materials and Methods Figs. S1 to S37 Tables S1 to S4 Published 18 November 2005, Science 310, 1166 (2005) DOI: /science

2 Materials and Methods for Porous, Crystalline Covalent Organic Frameworks Adrien P. Côté, Annabelle I. Benin, Nathan W. Ockwig, Michael O Keeffe, Adam J. Matzger, Omar M. Yaghi, * Materials Design and Discovery Group Department of Chemistry University of Michigan 930 North University Avenue Ann Arbor, Michigan, , USA Tel: , Fax: * oyaghi@umich.edu Department of Chemistry and Biochemistry Arizona State University Tempe, Arizona, , USA Materials and Methods Table of Contents Section S1 Section S2 Section S3 Section S4 Full synthetic procedures for the preparation of COF-1 and COF-5 and activation methods for gas adsorption measurements FT-IR Spectroscopy of Starting Materials, Model Compounds, and COFs Scanning Electron Microscopy Imaging (SEM) and Energy Dispersive X-ray (EDX) analysis of COF-1 and COF-5 11 B MAS and 13 C CP-MAS Nuclear Magnetic Resonance Studies for COF-1 and COF-5 S2 S5 S21 S23 Section S5 Structural Models and X-ray Analyses S26 Section S6 Low Pressure (0 1.0 bar) Gas Adsorption Measurements for COF-1 and COF-5 at 77, 87, and 293 K S33 Section S7 Thermalgravimetry S46 Section S8 Mass spectrum of guests extracted from COF-5 prior to gas adsorption analysis S48 S1

3 Materials and Methods Section S1: Full synthetic procedures for the preparation of COF-1 and COF-5 and activation methods for gas adsorption measurements. General Synthetic Procedures: All starting materials and solvents, unless otherwise noted, were obtained from the Aldrich Chemical Co. and used with out further purification. Transfer of all reagents was performed in an ambient laboratory air atmosphere with no precautions taken to exclude oxygen or atmospheric moisture. Pyrex glass tubes charged with reagents and flash frozen with LN 2 were evacuated using a Schlenk line by fitting the open end of the tube inside a short length of standard butyl rubber hose that was further affixed to a ground glass tap which could be closed to isolate this assembly from the dynamic vacuum when the desired internal pressure was reached. Tubes were then sealed under this static vacuum using an oxygen-propane torch. Sealing the tubes at 150(5) mtorr leads to optimal yields and crystallinity for both COFs, outside this pressure range yields diminished slightly at lower pressures and notably at higher pressures. We rationalize this observation on the fraction of H 2 O that becomes volatilized into the headspace of the tube thereby shifting the equilibrium of the reaction either towards amorphous products (lower pressures) and starting material (higher pressures). Synthesis of COF-1. A Pyrex tube measuring o.d. i.d. = 10 8 mm 2 was charged with 1,4-benzene diboronic acid (BDBA) (25 mg, 0.15 mmol, Aldrich) and 1 ml of a 1:1 v:v solution of mesitylene:dioxane. The tube was flash frozen at 77 K (LN 2 bath), evacuated to an internal pressure of 150 mtorr and flame sealed. Upon sealing the length of the tube was reduced to 18 cm. The reaction mixture was heated at 120 ºC for 72 h yielding a white solid at bottom of the tube which was isolated by filtration and washed with acetone (30 ml). Yield: 17 mg, 71 % for (C 3 H 2 BO) 6 (C 9 H 12 ) 1. Anal. Calcd. for (C 3 H 2 BO) 6 (C 9 H 12 ) 1 : C, 63.79; H, Found: C, 56.76; H, Following guest S2

4 removal: Anal. Calcd. for C 3 H 2 BO: C, 55.56; H, Found: C, 51.26; H, Note: organoboron compounds typically give lowered carbon values in elemental microanalysis due to the formation of non-combustible boron carbide byproducts. Synthesis of COF-5. A Pyrex tube measuring o.d. i.d. = 10 8 mm 2 was charged with 1,4-benzene diboronic acid (BDBA) (25 mg, 0.15 mmol, Aldrich), 2,3,6,7,10,11- hexahydroxytriphenylene [(HHTP) 16 mg, mmol, TCI] and 1 ml of a 1:1 v:v solution of mesitylene:dioxane. The tube was flash frozen at 77 K (LN 2 bath) and evacuated to an internal pressure of 150 mtorr and flame sealed. Upon sealing the length of the tube was reduced to 18 cm. The reaction mixture was heated at 100 ºC for 72 h to yield a free flowing gray-purple powder. Note that the purple color arises from oxidation of a small fraction HHTP which exhibits a very large extinction coefficient and is therefore very highly colored. This side product becomes incorporated within the pores imparting the purple color to the as synthesized form of COF-5. Following guest removal (see Adsorption Section below) COF-5 is obtained as a light gray solid. Yield: 15 mg, 73 % for C 9 H 4 BO 2 following guest removal. Anal. Calcld. for C 9 H 4 BO 2 : C, 69.67; H, Found: C, 66.48; H, Note: organoboron compounds typically give lowered carbon values in elemental microanalysis due to the formation of noncombustible boron carbide byproducts. No evidence for the formation of COF-1 was observed. Note that reaction of BDBA alone at 100 ºC to form COF-1 is slow where after 168 h COF-1 it is obtained in only 25 % yield. Activation of samples for gas adsorption measurements. COF-1: A 50 mg sample of COF-1 was heated to 150 o C under dynamic vacuum for 12 h. The sample was backfilled with nitrogen and then transferred in an air atmosphere to the required vessel for S3

5 gas adsorption measurements. COF-5: A 50 mg sample of COF-5 was placed in a 5 ml glass vial which was subsequently filled with HPLC grade (Aldrich) acetone. After 2 hours of exchange at room temperature the majority of the now yellow-purple acetone phase was decanted and the vial refreshed with acetone. After 12 hours the solvent was decanted again and the solid washed with acetone (3 ä 3 ml) and left to air dry in a desiccator (CaSO 4 ) for 2 hours and then evacuated for 12 h under dynamic vacuum at ambient temperature. Following evacuation, the sample was back-filled with nitrogen and then transferred in an air atmosphere to the required vessel for gas adsorption measurements. S4

6 Materials and Methods Section S2: FT-IR Spectroscopy of Starting Materials, Model Compounds, and COFs FT-IR spectra of starting materials and COFs were obtained as KBr pellets using Nicolet 400 Impact spectrometer. Assignment and analysis of infrared absorption bands of starting materials, model compounds, and COF products are presented in this section. Discussion pertaining to the IR spectral relationships between these compounds is offered as support for the formation of the covalently linked extended solids. Figure S1: FT-IR spectrum of benzene 1,4-diboronic acid (BDBA). S5

7 Figure S2: FT-IR spectrum of triphenylboroxine (COF-1 model compound). S6

8 Figure S3: FT-IR spectrum of COF-1 as synthesized. S7

9 Table S1: Peak assignments for FT-IR spectrum of COF-1. Notes are provided to correlate the spectra of starting material and model compound to that of COF-1. Peak (cm -1 ) Assignment and Notes (w) O H stretch from or end B(OH) 2 groups at the surface of crystallites (w) Aromatic C H stretch from phenyl group of COF-1; cf. band from benzene 1,4-diboronic acid at (w) (w) Aromatic C H stretch from phenyl group of COF-1; cf. band from benzene 1,4-diboronic acid at (w) (w) Aromatic C H stretch from mesitylene guest molecule. Characteristic methyl group C H stretching band. Not present in benzene 1,4- diboronic acid starting material nor in FT-IR spectrum of COF-1 following removal of guests (w) Methyl C H stretch from mesitylene guest molecule. Characteristic methyl group C H stretching band. Not present in benzene 1,4- diboronic acid starting material nor in FT-IR spectrum of COF-1 following removal of guests (w) Methyl C H stretch from mesitylene guest molecule. Characteristic methyl group C H stretching band. Not present in benzene 1,4- diboronic acid starting material nor in FT-IR spectrum of COF-1 following removal of guests (w) C H overtone band of p-substituted benzene; also observed in spectrum of the benzene 1,4-diboronic acid starting material (w) Aromatic ring vibration mode (ν 8a ). Arises only in substituted benzenes and strong in asymmetrically substituted benzenes. Characteristic band. Note absence in benzene 1,4-diboronic acid (Fig. S1). Should be absent in COF-1 since it is a completely symmetric system. It is observed (although weak) due to the population of or end B(OH) 2 groups at the surface of the crystallites in COF-1 which imparts some asymmetry to the system. Band could also be assigned to a sum tone of two low lying fundamentals (e.g. p-xylene) (s) Phenyl ring C=C vibrational mode (ν 19a ). Characteristic band. Normally strong intensity. Could be overlapped with same band from mesitylene (s) Can be assigned as phenyl ring C=C vibrational mode (ν 19b ). Although in the correct region for a p-disubstituted system, its intensity is normally weak. Different position than in triphenyleboroxine model compound, but this is expected because positioning varies according to the substitution pattern of the phenyl ring. Band is also present in the benzene 1,4,-diboronic acid starting material (s) B O stretch (characteristic band for boroxine), also present in triphenylboroxine model compound (s) B O stretch, shifted by -10 cm -1 from characteristic band for boroxine (s) C C stretch, shifted by -10 cm -1 from band observed for triphenylboroxine model compound. S8

10 (m) C B stretch; could be overlapped with C C stretch. Shifted by -5 cm -1 from band observed for triphenylboroxine model compound, and is the same position as observed in benzene 1,4-diboronic acid starting material (w) C H in plane deformation band p-substituted benzene, in the same position observed for benzene 1,4-diboronic acid starting material (m) C H in plane deformation band for p-substituted benzene, shifted by -16 cm -1 from band observed for benzene 1,4-diboronic acid starting material (w) B C stretch characteristic boroxine compounds, shifted by -5 cm -1 from triphenylboroxine model compound (w) Possibly B C stretch or C H stretch (m) B C stretch observed in both model compounds and COF (w) C H out of plane deformation band for p-substituted benzene, also present, but stronger, in benzene 1,4-diboronic acid (m) This peak has previously been assigned in an earlier to a C H deformation mode, however the presence of this peak in the exact position in triphenylboroxine (model compound) makes this assignment questionable since these compounds have different aromatic ring systems. Nonetheless, a constant structural element between the two compounds, likely the invariant boroxine ring, accounts for this band (s) Out-of-plane deformation for B 3 O 3 unit (w) Out of plane phenyl ring deformation for p-substituted benzene S9

11 Figure S4: Stack plot comparing the FT-IR spectrum of benzene 1,4-diboronic acid (top) to COF-1 (bottom). S10

12 Figure S5: Stack plot comparing the FT-IR spectrum of triphenylboroxine (top) to COF- 1 (bottom). S11

13 Figure S6: Stack plot comparing the FT-IR spectrum of COF-1 before (bottom) and following (top) evacuation of included guests and gas adsorption experiments. S12

14 Figure S7: FT-IR spectrum of of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP). S13

15 Figure S8: FT-IR spectrum of 2-Phenyl-1,3,2-benzodioxaborole, model compound for COF-5. S14

16 Figure S9: FT-IR spectrum of as synthesized COF-5. S15

17 Table S2: Peak assignments for FT-IR spectrum of COF-5. Notes are provided to correlate the spectra of starting materials and model compound to that of COF-5. Peak (cm -1 ) Assignment and Notes (m) O H stretch from or end B(OH) 2 or OH groups at the surface of crystallites (w) Aromatic C H stretch from benzene 1,4-diboronic acid phenyl group of COF-5; cf. band from benzene 1,4-diboronic acid at (w) (w) (w) (w) C H stretching from included guest molecules and triphenylene building block (w) C=C stretch in typical region for fused aromatics. Also present in spectrum of triphenylene (m) Phenyl ring C=C vibrational mode (ν 19a ). Characteristic band. Normally strong intensity. Could be overlapped with same band from mesitylene. Shifted by -5 cm -1 from benzene 1,4-diboronic acid (m) C=C vibrational modes for triphenylene building block. These are (m) characteristic bands for triphenylene (s) B O stretch (characteristic band for boroxole), shifted by -25 cm -1 from model compound 1332 (s) B O stretch, shifted by -3 cm -1 from characteristic band for model compound (s) C O characteristic stretch for boroxoles; shifted by +5 cm -1 from model compound (m) C H in plane bending modes (m) (m) B C stretch, also present in model compound (m) C H out of plane bands for p-substituted aromatic (m) (w) C H out of plane band in region for 1,2,4,5-substituted aromatic (w) C H out of plane band in region for 1,2,4,5-substituted aromatic (m) C H out of plane band shifted by -5 cm -1 from hexahydroxytriphenylene (w) C H out of plane band shifted by -6 cm -1 from hexahydroxytriphenylene (w) unassigned S16

18 Figure S10: Stack plot comparing the FT-IR spectrum of COF-5 (bottom) with benzene 1,4-diboronic acid (BDBA) (top). S17

19 Figure S11: Stack plot comparing the FT-IR spectrum of COF-5 (bottom) with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) (top). S18

20 Figure S12: Stack plot comparing the FT-IR spectrum of COF-5 (bottom) with 2- Phenyl-1,3,2-benzodioxaborole (top). S19

21 Figure S13: Stack plot comparing the FT-IR spectrum of COF-5 before (bottom) and following (top) removal of included guests by acetone extraction and gas adsorption experiments. S20

22 Materials and Methods Section S3: Scanning Electron Microscopy Imaging (SEM) and Energy Dispersive X-ray (EDX) analysis of COF-1 and COF-5 For SEM imaging Both materials were dispersed over a sticky carbon surface adhered to a flat aluminum platform sample holder and then gold coated (ambient temperature, reduced 200 torr pressure in an argon atmosphere, sputtered for 60 s from a solid gold target at a current at 40 ma). Samples were analyzed using a Hitachi S3200N Scanning Electron Microscope equipped with Imaging-Everhart-Thornley & Robinson BSE Detectors and a XEDS - Noran UTW SiLi detector, and was operated in high vacuum mode using a 30 kv accelerating voltage. Multiple samples of COF-1 and COF-5 were surveyed. Only one unique morphology was apparent after exhaustive examination of a range of particle sizes that were deposited on the sample holder: clusters of oblong plates were observed for COF-1 (Figure S14) and piles deformed hexagonal plates observed for COF-5 (Figure S15). No evidence for the presence of other phases was observed for either sample. No degradation of either sample was apparent during analysis which typically lasted h per sample. For EDX analysis using Hitachi S3200N Scanning Electron Microscope of the samples were prepared in the same manner as above for SEM imaging excluding gold coating. Although the elemental compositions of COF-1 and COF-5 consist of atoms which lie outside the reliable range for quantification by EDX analysis, detection of (spurious) heaver elements (e.g. Si from reaction vessel) was not observed supporting that single phase materials have been isolated. S21

23 Figure S14: SEM image of COF-1 revealing the clusters oblong plates; scale is inset. 100 µm Figure S15: SEM image of COF-5 revealing the piles of deformed hexagonal plates; scale is inset. 25 µm S22

24 Materials and Methods Section S4: 11 B MAS and 13 C CP-MAS Nuclear Magnetic Resonance Studies for COF-1 and COF-5 Data were collected on a Bruker DSX 300 MHz Solid State NMR. Samples were packed in 5 mm ZrO 2 rotors and spun between khz during data collection. Standard pulse sequences were employed with s recycle times found to be optimal. Figure S16: Stack plot comparing the 11 B NMR spectra of COF-1, triphenylboroxine, and BDBA diboronic acid. Asterisks (*) indicate peaks arising from spinning side bands. x Intensity * * * * * * * COF1 triphenylboroxine diboronic acid PPM S23

25 Figure S17: Stack plot comparing the 11 B NMR spectra of COF-5, 2-Phenyl-1,3,2- benzodioxaborole, and BDBA diboronic acid. Asterisks (*) indicate peaks arising from spinning side bands. * * * * * * S24

26 Figure S18: 13 C CP-MAS NMR spectrum of COF-1 (top) vs. triphenylboroxine (bottom) evidencing the inclusion of mesitylene with observance of signature methyl single at 23.1 ppm. Asterisks (*) indicate peaks arising from spinning side bands. S25

27 Materials and Methods Section S5: Structural Models and X-ray Analyses Cerius 2 Modeling: Atomic positions in fractional coordinates of unit cell parameters calculated from Cerius 2 were used for model biased Le Bail extractions and illustrations depicted in manuscript. For both models a single benzene ring was placed at the centroids of the respective pores of COF-1 (1/3, 2/3, 3/4) and COF-5 (0, 0, 0) to represent guest molecules. For COF-5 guests were included at 15 % site occupancy to represent the random population of the mesopores by starting materials, solvent, and byproducts. Table S3: Fractional atomic coordinates for COF-1 and COF-5 calculated from Cerius 2 modeling. COF-1 COF-5 Hexagonal, P6 3 /mmc a = b = , c = Å Hexagonal, P6/mmm a = b = , c = Å atom x, y, z atom x, y, z B , , B , , B , , O , , O , , C , , O , , C , , C , , C , , C , , C , , C , , C , , C , , C , , C , , C , , C , , X-ray Data Collection, Unit Cell Determination, and Le Bail Extraction: Powder X-ray data were collected using a Bruker D8-Advance θ-2θ diffractometer in reflectance Bragg- Brentano geometry employing Ni filtered Cu Kα line focused radiation at 1600 W (40 kv, 40 ma) power and equipped with a Na(Tl) scintillation detector fitted a 0.2 mm S26

28 radiation entrance slit. Samples were mounted on zero background sample holders by dropping powders from a wide-blade spatula and then leveling the sample surface with a razor blade. Given that the particle size of the as synthesized samples were already found to be quite mono-disperse no sample grinding or sieving was used prior to analysis. The best counting statistics were achieved by collecting samples using a 0.02º 2θ step scan from º with an exposure time of 10 s per step. No peaks could be resolved from the baseline for 2θ > 50º data and was therefore not considered for further analysis. Unit cell determinations were carried out using the Powder-X software suite (PowderX: Windows-95 based program for powder X-ray diffraction data processing", C. Dong, J. Appl. Crystollogr. (1999), 32, 838) for peak selection and interfacing with the Treor (TREOR: A Semi-Exhaustive Trial-and-Error Powder Indexing Program for All Symmetries. Werner, P.-E., Eriksson, L. and Westdahl, M., J. Appl. Crystollogr. 18 (1985) 367) ab inito powder diffraction indexing program. Figure of merits were M 10 = 15 for COF-1 and M 9 = 18 for COF-5. An internal Si standard (NIST) was used to normalize peak positions. A low angle calibration of the instrument [using silver behenate (Gem Dugout) see: Huang T.C., Toraya H., Blanton T.N., Wu Y., J. Appl. Crystallogr., 1993, 26, 180] was also performed to improve the accuracy of data collected in this region. Table S4: Calculated and experimental unit cell parameters for COF-1 and COF-5. Unit cell Parameter Cerius2 Treor Le Bail COF-1, Hexagonal, P6 3 /mmc a = b (Å) (4) (1) c (Å) (3) 6.655(4) COF-5, Hexagonal, P6/mmm a = b (Å) (3) 29.70(1) c (Å) (2) 3.460(2) S27

29 Le Bail extractions were conducted using the GSAS program using data from 2θ = 3 50º for COF-1 and 2θ = 1.5 to 50º for COF-5. Backgrounds where hand fit with with six terms applying a shifted Chebyschev Polynomial. Both profiles where calculated starting with the unit cell parameters indexed from the raw powder patterns and the atomic positions calculated from Cerius 2. Using the model-biased Le Bail algorithm, F obs were extracted by first refining peak asymmetry with Gausian peak profiles, followed by refinement of polarization with peak asymmetry. Unit cells were then refined with peak asymmetry and polarization resulting in convergent refinements. Once this was achieved unit cell parameters were refined followed by zero-shift. Refinement of unit cell parameters, peak asymmetry, polarization and zero-shift were used for the final profiles. Table S5: Final statistics from Le Bail extractions of COF-1 and COF-5 PXRD data. COF-1 COF-5 R p wr p χ S28

30 Figure S19: PXRD pattern of COF-1 (top) compared to patterns calculated from Cerius 2 with the stacking of the layers in AB staggered arrangement with P6 3 /mmc space group symmetry (middle) and (bottom) in AA eclipsed stacking arrangement with P6/mmm. Note the pattern from the eclipsed model does not match the pattern of COF-1. COF-1 Staggered, matches pattern of COF-1 Eclipsed S29

31 Figure S20: PXRD pattern of COF-5 (top) compared to patterns calculated from Cerius 2 with the stacking of the layers in AB staggered arrangement with P6 3 /mmc space group symmetry (middle) and (bottom) in AA eclipsed stacking arrangement with P6/mmm. Note the pattern from the staggared model does not match the pattern of COF-5. COF-1 Staggered Eclipsed, matches pattern of COF S30

32 Figure S21: PXRD patterns of COF-1 following evacuation of guest molecules and gas adsorption measurements (top) and as synthesized (bottom) illustrating the shifting of layers which results upon guest removal. Note that the principle 100 and 002 diffraction peaks of COF-1 are retained. after guest removal and gas sorption before guest removal and gas sorption (as synthesized) S31

33 Figure S22: PXRD patterns of COF-5 following removal of guest molecules by acetone extraction and gas adsorption measurements (top) and as synthesized (bottom). after guest removal and gas sorption before guest removal and gas sorption (as synthesized) S32

34 Supplementary Section S6: Low Pressure (0 1.0 bar) Gas Adsorption Measurements for COF-1 and COF-5 at 77, 87, and 293 K Gas adsorption isotherms were measured volumetrically using a Quantachrome Autosorb-1 automated adsorption analyzer. A liquid nitrogen bath (77 K) was used for N 2 isotherms, an argon bath (87 K) was used for Ar isotherms. Micropore sorption data using CO 2 were collected a 273 K (ice water bath). The N 2, Ar, and CO 2 gases used were UHP grade. For measurement of the specific surface areas (A s, m 2 /g) the BET method was applied. Measured uptakes from Ar isotherms are slightly higher than for N 2, we however report the more conservative N 2 data in the manuscript for surface areas and pore volumes. The higher uptakes for Ar are likely do to its small size which allows more adatoms to bind into adsorption sites in the frameworks that are too small to accommodate nitrogen. For all isotherm plots below closed circles are used for adsorption data points and open circles are used to indicate desorption data points. The pore size distribution for COF-1 provided in the manuscript is a composite histogram NLDFT fitting of CO 2 and Ar isotherms. The 0-10 Å segment was taken from CO 2 data and the Å segement take from Ar data. They are the valid ranges for these NLDFT models and a composite figure was generated as the Ar model is not valid below 10 Å. S33

35 Figure S23: Nitrogen gas isotherm for COF-1 measured at 77 K Uptake (cm 3 g -1 ) P/P 0 S34

36 Figure S24: Nitrogen gas isotherm for COF-5 measured at 77 K Uptake (cm 3 g -1 ) P/P 0 S35

37 Figure S25: Argon gas isotherm for COF-1 measured at 87 K Uptake (cm 3 g -1 ) P/P 0 S36

38 Figure S26: Argon gas isotherm for COF-5 measured at 87 K Uptake (cm 3 g -1 ) P/P 0 S37

39 Figure S27: BET plot for COF-1 calculated from nitrogen adsorption data. 1.60E E E-04 (P/P 0 )/N(1-P/P 0 ) 1.00E E E E E E+00 R 2 = S A = 711 m 2 g P/P 0 S38

40 Figure S28: BET plot for COF-5 calculated from nitrogen adsorption data. 3.00E E-01 1/(W((P 0 /P)-1) 2.00E E E E E+00 R 2 = S A = 1590 m 2 g P/P 0 S39

41 Figure S29: BET plot for COF-1 calculated from argon adsorption data. 5.00E E E E-01 1/(W((P 0 /P)-1) 3.00E E E E E E E+00 R 2 = S A = 710 m 2 g P/P 0 S40

42 Figure S30: BET plot for COF-5 calculated from argon adsorption data. 3.00E E-01 1/(W((P 0 /P)-1) 2.00E E E E E+00 R 2 = S A = 1723 m 2 g P/P 0 S41

43 Figure S31: De Boer t-plot for COF Uptake (cm 3 g -1 ) R 2 = De Boer Statistical Thickness (Å) S42

44 Figure S32: Carbon dioxide isotherm for COF-1 measured at 273 K used for NLDFT modeling and pore size distribution calculations. The calculated NLDFT isotherm (carbon slit pore model) is overlaid as open triangles and fitting error indicated Uptake (cm 3 g -1 ) Fitting Error = % P/P 0 S43

45 Figure S33: Argon isotherm for COF-1 measured at 87 K used for NLDFT modeling and pore size distribution calculations. The calculated NLDFT isotherm (carbon slit pore model) is overlaid as open triangles and fitting error indicated Uptake (cm 3 g -1 ) Fitting Error = 1.01 % P/P 0 S44

46 Figure S34: Argon isotherm for COF-5 measured at 87 K used for NLDFT modeling and pore size distribution calculations. The calculated NLDFT isotherm (silica cylindrical pore model) is overlaid as open triangles and fitting error indicated Uptake (cm 3 g -1 ) Fitting Error = 0.83 % P/P 0 S45

47 Supplementary Section S7: Thermalgravimetry Samples were run on a TA Instruments Q-500 series thermal gravimetric analyzer with samples held in platinum pans in an nitrogen atmosphere. A 5 Kmin -1 ramp rate was used and samples were in tested in their as synthesized form following washing products isolated from reactions with acetone. Figure S35: TGA trace for COF-1 S46

48 Figure S36: TGA trace for COF-5. S47

49 Supplementary Section S8: Mass spectrum of guests extracted from COF-5 prior to gas adsorption analysis. Figure S37: EI-MS spectrum of acetone supernatant from COF-5 activation evidencing the extraction of BDBC (m/z = 167) and HHTP (m/z = 324.1). S48