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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. E-mail: [email protected]
Published 18 November 2005, Science 310, 1166 (2005)
DOI: 10.1126/science.1120411
This PDF file includes:
Materials and Methods Figs. S1 to S37 Tables S1 to S4
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, 48109-1055, USA
Tel: 734-615-2146, Fax: 734-615-9751
*Email: [email protected]
‡ Department of Chemistry and Biochemistry Arizona State University
Tempe, Arizona, 85287-1604, USA
Materials and Methods Table of Contents Section S1 Full synthetic procedures for the preparation of COF-1 and COF-5
and activation methods for gas adsorption measurements S2
Section S2 FT-IR Spectroscopy of Starting Materials, Model Compounds, and
COFs S5
Section S3 Scanning Electron Microscopy Imaging (SEM) and Energy
Dispersive X-ray (EDX) analysis of COF-1 and COF-5 S21
Section S4 11B MAS and 13C CP-MAS Nuclear Magnetic Resonance Studies for
COF-1 and COF-5 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
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 LN2 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 H2O 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 mm2 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 (LN2 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 (C3H2BO)6•(C9H12)1. Anal. Calcd. for
(C3H2BO)6•(C9H12)1: C, 63.79; H, 4.77. Found: C, 56.76; H, 4.34. Following guest
S2
removal: Anal. Calcd. for C3H2BO: C, 55.56; H, 3.10. Found: C, 51.26; H, 2.91. 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 mm2 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, 0.050 mmol, TCI] and 1 mL of a 1:1 v:v
solution of mesitylene:dioxane. The tube was flash frozen at 77 K (LN2 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 C9H4BO2 following guest removal. Anal. Calcld. for C9H4BO2: C,
69.67; H, 2.60. Found: C, 66.48; H, 2.81. Note: organoboron compounds typically give
lowered carbon values in elemental microanalysis due to the formation of non-
combustible 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 oC under dynamic vacuum for 12 h. The sample was back-
filled with nitrogen and then transferred in an air atmosphere to the required vessel for
S3
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 (CaSO4) 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
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
Figure S2: FT-IR spectrum of triphenylboroxine (COF-1 model compound).
S6
Figure S3: FT-IR spectrum of COF-1 as synthesized.
S7
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
3429.7 (w) O—H stretch from or end –B(OH)2 groups at the surface of crystallites. 3078.4 (w) Aromatic C—H stretch from phenyl group of COF-1; cf. band from
benzene 1,4-diboronic acid at 3072.3 (w). 3037.6 (w) Aromatic C—H stretch from phenyl group of COF-1; cf. band from
benzene 1,4-diboronic acid at 3047.8 (w) 3017.3 (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.
2915.4 (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.
2859.4 (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.
1953.0 (w) C—H overtone band of p-substituted benzene; also observed in spectrum of the benzene 1,4-diboronic acid starting material.
1611.9 (w) Aromatic ring vibration mode (ν8a). 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).
1515.1 (s) Phenyl ring C=C vibrational mode (ν19a). Characteristic band. Normally strong intensity. Could be overlapped with same band from mesitylene.
1403.1 (s) Can be assigned as phenyl ring C=C vibrational mode (ν19b). 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.
1377.7 (s) B—O stretch (characteristic band for boroxine), also present in triphenylboroxine model compound.
1342.0 (s) B—O stretch, shifted by -10 cm-1 from characteristic band for boroxine. 1301.3 (s) C—C stretch, shifted by -10 cm-1 from band observed for
triphenylboroxine model compound.
S8
1260.5 (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.
1174.2 (w) C—H in plane deformation band p-substituted benzene, in the same position observed for benzene 1,4-diboronic acid starting material.
1112.9 (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.
1087.4 (w) B—C stretch characteristic boroxine compounds, shifted by -5 cm-1 from triphenylboroxine model compound.
1067.0 (w) Possibly B—C stretch or C—H stretch 1026.3 (m) B—C stretch observed in both model compounds and COF-5. 848.1 (w) C—H out of plane deformation band for p-substituted benzene, also
present, but stronger, in benzene 1,4-diboronic acid. 761.5 (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.
710.6 (s) Out-of-plane deformation for B3O3 unit. 664.8 (w) Out of plane phenyl ring deformation for p-substituted benzene
S9
Figure S4: Stack plot comparing the FT-IR spectrum of benzene 1,4-diboronic acid (top)
to COF-1 (bottom).
S10
Figure S5: Stack plot comparing the FT-IR spectrum of triphenylboroxine (top) to COF-
1 (bottom).
S11
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
Figure S7: FT-IR spectrum of of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP).
S13
Figure S8: FT-IR spectrum of 2-Phenyl-1,3,2-benzodioxaborole, model compound for
COF-5.
S14
Figure S9: FT-IR spectrum of ‘as synthesized COF-5.’
S15
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
3394.1 (m) O—H stretch from or end –B(OH)2 or –OH groups at the surface of crystallites.
3078.4 (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 3072.3 (w).
2976.5 (w) 2930.7 (w) 2859.4 (w)
C—H stretching from included guest molecules and triphenylene building block.
1637.3 (w) C=C stretch in typical region for fused aromatics. Also present in spectrum of triphenylene.
1525.3 (m) Phenyl ring C=C vibrational mode (ν19a). Characteristic band. Normally strong intensity. Could be overlapped with same band from mesitylene. Shifted by -5 cm-1 from benzene 1,4-diboronic acid.
1494.8 (m) 1448.9 (m)
C=C vibrational modes for triphenylene building block. These are characteristic bands for triphenylene.
1347 (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.
1245.3 (s) C—O characteristic stretch for boroxoles; shifted by +5 cm-1 from model compound.
1163.8 (m) 1082.3 (m)
C—H in plane bending modes
1026.3 (m) B—C stretch, also present in model compound 858.3 (m) 832.8 (m)
C—H out of plane bands for p-substituted aromatic.
802.3 (w) C—H out of plane band in region for 1,2,4,5-substituted aromatic 736.1 (w) C—H out of plane band in region for 1,2,4,5-substituted aromatic 664.8 (m) C—H out of plane band shifted by -5 cm-1 from
hexahydroxytriphenylene 613.9 (w) C—H out of plane band shifted by -6 cm-1 from
hexahydroxytriphenylene 542.6 (w) unassigned
S16
Figure S10: Stack plot comparing the FT-IR spectrum of COF-5 (bottom) with benzene
1,4-diboronic acid (BDBA) (top).
S17
Figure S11: Stack plot comparing the FT-IR spectrum of COF-5 (bottom) with
2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) (top).
S18
Figure S12: Stack plot comparing the FT-IR spectrum of COF-5 (bottom) with 2-
Phenyl-1,3,2-benzodioxaborole (top).
S19
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
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 1 - 1.5 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
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
Materials and Methods Section S4: 11B MAS and 13C 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 ZrO2 rotors and spun between 5.0 – 8.0 kHz during data collection.
Standard pulse sequences were employed with 1.0 - 1.5 s recycle times found to be
optimal.
Figure S16: Stack plot comparing the 11B NMR spectra of COF-1, triphenylboroxine,
and BDBA diboronic acid. Asterisks (*) indicate peaks arising from spinning side bands.
x106
300
200
100
0
-100
-200
Inte
nsity
-200-1000100200PPM
COF1
triphenylboroxine
*
**
**
*
*
diboronic acid
S23
Figure S17: Stack plot comparing the 11B NMR spectra of COF-5, 2-Phenyl-1,3,2-
benzodioxaborole, and BDBA diboronic acid. Asterisks (*) indicate peaks arising from
spinning side bands.
**
**
**
S24
Figure S18: 13C 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
Materials and Methods Section S5: Structural Models and X-ray Analyses Cerius2 Modeling: Atomic positions in fractional coordinates of unit cell parameters
calculated from Cerius2 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 Cerius2
modeling.
COF-1 COF-5
Hexagonal, P63/mmc a = b = 15.6529, c = 6.7005 Å
Hexagonal, P6/mmm a = b = 30.0198, c = 3.4040 Å
atom x, y, z atom x, y, z B1 0.05772, 0.11543, 0.25000 B1 0.11357, 0.55679, 0.50000 B2 0.44466, 0.72233, 0.25000 O1 0.61305, 0.14429, 0.50000 O1 0.11133, 0.05567, 0.25000 C1 0.94617, 0.47308, 0.50000 O2 0.38900, 0.77800, 0.25000 C2 0.47312, 0.02688, 0.50000 C1 0.11184, 0.38361, 0.25000 C3 0.61950, 0.19328, 0.50000 C2 0.21864, 0.43728, 0.25000 C4 0.66641, 0.23896, 0.50000 C3 0.21837, 0.27685, 0.25000 C5 0.66687, 0.28621, 0.50000 C4 0.11030, 0.88970, 0.25000 C6 0.02886, 0.05722, 0.50000 C5 0.38900, 0.77800, 0.75000 C7 0.05567, 0.02783, 0.50000 C6 0.44466, 0.72233, 0.75000
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
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 1.5 – 60º 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 M10 =
15 for COF-1 and M9 = 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, P63/mmc a = b (Å) 15.6529 15.056(4) 15.420(1)
c (Å) 6.7005 6.585(3) 6.655(4) COF-5, Hexagonal, P6/mmm
a = b (Å) 30.0198 29.74 (3) 29.70(1) c (Å) 3.4040 3.1(2) 3.460(2)
S27
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 Cerius2. Using the model-biased Le Bail algorithm, Fobs
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
Rp 0.0870 0.0476 wRp 0.1122 0.0635 χ2 10.43 18.46
S28
Figure S19: PXRD pattern of COF-1 (top) compared to patterns calculated from Cerius2
with the stacking of the layers in AB staggered arrangement with P63/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.
3 10 20 30 40 50 60
COF-1
Staggered, matches pattern of COF-1
Eclipsed
S29
Figure S20: PXRD pattern of COF-5 (top) compared to patterns calculated from Cerius2
with the stacking of the layers in AB staggered arrangement with P63/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.
3 10 20 30 40 50 6
COF-1
Staggered
Eclipsed, matches pattern of COF-5
S30
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.
3 10 20 30 40 50 6
before guest removal and gas sorption (as synthesized)
after guest removal and gas sorption
S31
Figure S22: PXRD patterns of COF-5 following removal of guest molecules by acetone
extraction and gas adsorption measurements (top) and as synthesized (bottom).
3 10 20 30 40 50
before guest removal and gas sorption (as synthesized)
after guest removal and gas sorption
S32
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 N2
isotherms, an argon bath (87 K) was used for Ar isotherms. Micropore sorption data
using CO2 were collected a 273 K (ice water bath). The N2, Ar, and CO2 gases used were
UHP grade. For measurement of the specific surface areas (As, m2/g) the BET method
was applied. Measured uptakes from Ar isotherms are slightly higher than for N2, we
however report the more conservative N2 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 CO2 and Ar isotherms. The 0-10 Å segment was taken from
CO2 data and the 10-100 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
Figure S23: Nitrogen gas isotherm for COF-1 measured at 77 K.
0
50
100
150
200
250
300
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
P/P0
Upt
ake
(cm
3 g-1
)
S34
Figure S24: Nitrogen gas isotherm for COF-5 measured at 77 K.
0
100
200
300
400
500
600
700
800
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
P/P0
Upt
ake
(cm
3 g-1
)
S35
Figure S25: Argon gas isotherm for COF-1 measured at 87 K.
0
50
100
150
200
250
300
350
400
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1P/P0
Upt
ake
(cm
3 g-1
)
S36
Figure S26: Argon gas isotherm for COF-5 measured at 87 K.
0
200
400
600
800
1000
1200
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
P/P0
Upt
ake
(cm
3 g-1)
S37
Figure S27: BET plot for COF-1 calculated from nitrogen adsorption data.
R2 = 0.9999
0.00E+00
2.00E-05
4.00E-05
6.00E-05
8.00E-05
1.00E-04
1.20E-04
1.40E-04
1.60E-04
0 0.02 0.04 0.06 0.08 0.1 0.12P/P0
(P/P
0)/N
(1-P
/P0)
S A = 711 m2 g-1
S38
Figure S28: BET plot for COF-5 calculated from nitrogen adsorption data.
R2 = 0.9946
0.00E+00
5.00E-02
1.00E-01
1.50E-01
2.00E-01
2.50E-01
3.00E-01
0 0.02 0.04 0.06 0.08 0.1 0.12P/P0
1/(W
((P0/P
)-1)
S A = 1590 m2 g-1
S39
Figure S29: BET plot for COF-1 calculated from argon adsorption data.
R2 = 0.9999
0.00E+00
5.00E-02
1.00E-01
1.50E-01
2.00E-01
2.50E-01
3.00E-01
3.50E-01
4.00E-01
4.50E-01
5.00E-01
0 0.02 0.04 0.06 0.08 0.1 0.12P/P0
1/(W
((P0/P
)-1)
S A = 710 m2 g-1
S40
Figure S30: BET plot for COF-5 calculated from argon adsorption data.
R2 = 0.9981
0.00E+00
5.00E-02
1.00E-01
1.50E-01
2.00E-01
2.50E-01
3.00E-01
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14P/P0
1/(W
((P0/P
)-1)
S A = 1723 m2 g-1
S41
Figure S31: De Boer t-plot for COF-1
R2 = 0.9842
780
790
800
810
820
830
840
850
860
870
880
0 2 4 6 8 10 12 14 1De Boer Statistical Thickness (Å)
Upt
ake
(cm
3 g-1
)
6
S42
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.
0
5
10
15
20
25
30
0 0.005 0.01 0.015 0.02 0.025 0.03
P/P0
Upt
ake
(cm
3 g-1)
Fitting Error = 0.032 %
S43
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.
0
50
100
150
200
250
300
350
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
P/P0
Upt
ake
(cm
3 g-1
)
Fitting Error = 1.01 %
S44
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.
0
100
200
300
400
500
600
700
800
900
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
P/P0
Upt
ake
(cm
3 g-1
)
Fitting Error = 0.83 %
S45
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
Figure S36: TGA trace for COF-5.
S47
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