Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is © The Royal Society of Chemistry 2014
Electronic Supplementary Information
Facile synthesis of azo-linked porous organic frameworks via reductive homocoupling
for selective CO2 capture
Jingzhi Lu and Jian Zhang*
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588, USA
E-Mail: [email protected]
Table of Contents
1. Materials and measurements S2
2. General synthetic procedures S3
3. FT-IR spectra S9
4. 13C NMR spectra S13
5. Powder X-ray diffraction S16
6. Thermal gravimetric analysis of azo-POFs S17
7. Additional gas adsorption data for azo-POFs and ene-POFs S18
S1 1. Materials and measurements
Trityl chloride (97%), aniline (99.5%), isopentyl nitrite (96%), 50% hypophosphorous acid solution, fuming nitric acid (99.5%) and tetrahydrofuran (THF, 99%) were obtained from Sigma- Aldrich. Tetraphenylethylene (98%), Sodium hydroxide (pellet, 98%), zinc powder (99.9%) and N,N-dimethylformamide (DMF, 99.9%) were purchased from Alfa Aesar. Acetic acid (glacial), concentrated hydrochloride acid and concentrated sulfuric acid were obtained from Fisher Scientific. Ethanol (200 proof) was purchased from Decon Lab. All chemicals were used without purification unless otherwise noted.
Solution NMR was performed on either a Bruker FT-NMR spectrometer (400 MHz) or a Bruker FT-NMR spectrometer (300 MHz). Solid-state CP/MAS 13C NMR spectra were collected on a Bruker Avance III three-channel spectrometer. Infrared spectroscopy was performed on a Nicolet Avatar 360 FT-IR. UV-Vis absorption spectra were obtained on an Aligent Cary 300 facility with DRA-CA-30I solid-state sample holder. Thermogravimetric Analysis (TGA) was performed on a Perkin Elmer STA 6000 Thermogravimetric Analyzer, heated from 30 °C to 1000 °C at a rate of 10 °C/minute under N2 atmosphere. X-ray diffraction patterns were acquired from 3 to 80° by a Rigaku Multiflex Diffractometer.
Gas adsorption isotherms were collected using a Micromeritics ASAP 2020-accelerated surface area and porosimetry analyser after the samples had been degassed at 150 °C for 8 h under vacuum. Before the every adsorption measurement, the samples were degassed further at 150 °C for 5 h.
S2 2. General Synthetic Routes
NO2
1) Aniline 1) H2SO4/EtOH Nitric acid Cl O2N NO2 2) 2M HCl/MeOH 2) Isopentyl nitrite 3) 30% H3PO2
NO2 1 2
Synthesis of tetraphenylmethane (1). Prepared by a known procedure.1 : Trityl chloride (15 g, 53.8 mmol) was mixed with aniline (13.7 g, 147.1 mmol) in a round bottom flask charged with argon. The mixture was slowly heated to 200 °C for 5 minutes and cooled to room temperature. The obtained solid was crushed into small pieces and heated with 100 ml of 2M HCl and 90 ml of methanol at 100 °C for 2 hours. After filtration, the gray solid was washed with 100 ml water and 100 ml methanol and dried under vacuum. The dried gray solid was suspended in 120 ml of ethanol and 16.5 ml concentrated sulfuric acid and cooled to -10 °C. After 12 ml of isopentyl nitrite was slowly added, the mixture was stirred for another 1 hour. 40 ml of 30 % hypophosphorous acid was slowly added at -10 °C and the mixture was heated to 50 °C for 2 hours. An olive colored solid was obtained after filtration, followed by washing with ethanol and 1,4-dioxane to get tetraphenylmethane as a light yellow solid in 80% yield. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.17 -7.06 (m, 20H, Ar-H).
Synthesis of tetrakis(4-nitrophenyl)methane (TNPM, 2). Prepared by a known procedure.1 13 ml of fuming nitric acid was added in a round bottom flask and cooled to -10 °C. Tetraphenylmethane (5 g, 15.6 mmol) was added to the pre-cooled fuming nitric acid in small portions under vigorous stirring. After addition, 6 ml of acetic anhydride and 8 ml of glacial acetic acid were added drop-wise and the mixture was stirred for about 15 minutes. Then, 16 ml glacial acetic acid was added to dilute the mixture. After filtration, the yellow solid was washed with plenty of water to get light yellow product in 40% yield. 1H NMR (300 MHz, DMSO) δ (ppm): 8.51 (d, J = 8.7 Hz, 8H, Ar-H), 7.85 (d, J = 8.7 Hz, 8H, Ar-H).
NO2 NH2
Raney Ni
N2H4 H2O O2N NO2 H2N NH2 THF
NO2 NH2 2 3 Synthesis of tetrakis(4-aminophenyl)methane (TAPM, 3). Prepared by a known procedure.1 Tetrakis(4-nitrophenyl)methane (500 mg, 1 mmol) was dissolved in 10 ml THF. Raney nickel (~2 g) and hydrazine monohydrate (670 mg, 13.4 mmol) were added to the solution carefully and the reaction mixture was heated to reflux for 2 hours. After the reaction mixture was cooled to room temperature, the nickel was filtered off and the solvent was evaporated under reduced pressure to get off-white solid in 86 % yield. 1H NMR (300 MHz, DMSO) δ (ppm): 6.67 (d, J =8.9 Hz, 8H, Ar-H), 6.38 (d, J = 8.9 Hz, 8H, Ar-H), 4.83 (s, 8H, Ar-NH2)
S3 O2N NO2 H2N NH2
Raney Ni
Nitric acid N2H4 H2O
Acetic acid THF
O2N NO2 H2N NH2
4 5 Synthesis of 1,1,2,2-tetrakis(4-nitrophenyl)ethene (TNPE, 4). Prepared by a known procedure.2 A mixture of 30 ml of acetic acid and 30 ml fuming nitric acid was cooled to 0 °C by ice bath and 1,1,2,2-tetraphenylethene (3g, 9 mmol) was added in small portions. After addition, the ice bath was removed and the mixture was stirred at room temperature for 3 hours. The resulting brown solution was poured into 300 g ice water to get light yellow precipitation. The precipitation was filtered off and recrystalize from 1,4-dioxane to get light yellow crystal in 50% yield. 1H NMR (300 MHz, DMSO) δ (ppm): 8.10 (d, J = 8.7 Hz, 8H, Ar-H), 7.36 (d, J = 8.7 Hz, 8H, Ar-H).
Synthesis of 1,1,2,2-tetrakis(4-aminophenyl)ethene (TAPE, 5). Synthetic method was adapted from the preparation of TAPM. 1,1,2,2-tetrakis(4-nitrophenyl)ethene (525 mg, 1 mmol) was dissolved in 10 ml THF. Raney nickle (~2 g) and hydrazine monohydrate (670 mg, 13.4 mmol) were added to the solution carefully and the reaction mixture was heated to reflux for 2 hours. After the reaction mixture was cooled to room temperature, the nickle was filtered off and the solvent was evaporated under reduced pressure to get light yellow solid in 84 % yield. 1H NMR (300 MHz, DMSO) δ (ppm): 6.57 (d, J =8.7 Hz, 8H, Ar-H), 6.25 (d, J = 8.7 Hz, 8H, Ar-H), 4.84 (s, 8H, Ar-NH2)
Br
Br2 Br Br
Br 6
Synthesis of tetrakis(4-bromophenyl)methane (TBPM, 6). Prepared by a known procedure.3 Bromine (16 ml, 49.75 g, 312.5 mmol) was loaded in a round-bottom flask. Under vigorous stirring, tetraphenylmethane (5 g, 15.6 mmol) was added to the flask in small portions in five minutes at room temperature. After the completion of the addition, the mixture was stirred for another 20 minutes at room temperature and was cooled to -78 oC by acetone-dry ice bath. After 40 ml of ethanol was slowly added, the cooling bath was removed and the mixture was stirred overnight. The precipitate was collected by filtration and washed with aqueous sodium hydrogensulfite solution, water and ethanol. The solid was dry in vacuo and the product was 1 obtained as a light yellow solid in 80 % yield. H NMR (300 MHz, CDCl3) δ (ppm): 7.41 (d, J = 8.7 Hz, 8H, Ar-H), 7.02 (d, J = 8.7 Hz, 8H, Ar-H).
S4 Br Br
Br2
Br Br 7
Synthesis of 1,1,2,2-tetrakis(4-bromophenyl)ethene (TBPE, 7). Prepared by a known procedure.4 Bromine (8 ml, 25 g, 156.3 mmol) was loaded in a round-bottom flask. Under vigorous stirring, tetraphenylethene (5 g, 15.6 mmol) was added to the flask in small portions in five minutes at room temperature. After the completion of the addition, the mixture was stirred for another 16 h at room temperature and was cooled to -78 oC by acetone-dry ice bath. After 40 ml of ethanol was slowly added, the cooling bath was removed and the mixture was stirred overnight. The precipitate was collected by filtration and washed with aqueous sodium hydrogensulfite solution, water and ethanol. After the solid was recrystallized from mixture of benzene and ethanol, the product was obtained as a white solid in 55 % yield. 1H NMR (300 MHz, CDCl3) δ (ppm): 7.28 (d, J = 8.4 Hz, 8H, Ar-H), 6.86 (d, J = 8.4 Hz, 8H, Ar-H)
NH 2 N N N N Nitrosobenzne
H2N NH2 Acetic acid N N N N NH2 3
Model compound 1
Synthesis of model compound 1: Tetrakis(4-aminophenyl)methane (200 mg, 0.53 mmol) and nitrosobenzene (340 mg, 3.18 mmol) were dissolved in 10ml of glacial acetic acid. The solution was heated at 80 °C for 18 hours and cooled to room temperature. The orange precipitate was filtered and washed with water and methanol to get orange solid in 49 % yield. 1H NMR (400 13 MHz, CDCl3) δ (ppm): 7.94-7.88 (m, 16H, Ar-H), 7.56-7.52 (m, 20H, Ar-H). C NMR (100 MHz, CDCl3) δ (ppm): 152.7, 151.0, 148.7, 131.7, 131.1, 129.1, 122.9, 122.4, 65.3. Calc. MS: 736.3063, MALDI found [M+H]+: 737.3146.
S5 N H2N NH2 N N N Nitrosobenzne
Acetic acid N N N N H2N NH2
5 Model compound 2 Synthesis of model compound 2: 1,1,2,2-tetrakis(4-aminophenyl)ethene (210 mg, 0.53 mmol) and nitrosobenzne (340 mg, 3.18 mmol) were dissolved in 10ml of glacial acetic acid. The solution was heated at 80 °C for 18 hours and cooled to room temperature. The orange precipitate was filtered and washed with water and methanol to get orange solid in 33 % yield. 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.90 (d, J = 8.2 Hz, 8H, Ar-H), 7.77 (d, J = 8.4 Hz, 8H, Ar- 13 H), 7.54-7.47 (m, 12H, Ar-H), 7.31 (d, J = 8.4 Hz, 8H, Ar-H). C NMR (100 MHz, CDCl3) δ (ppm): 152.7, 151.3, 145.8, 141.6, 132.3, 131.0, 129.1, 122.9, 122.7. Calc. MS: 748.3063, MALDI found [M+H]+: 749.3039.
N NO2 N
Zinc powder NaOH (aq.) N O2N NO2 N N THF/DMF N
NO N 2 N 2
azo-POF-1
Synthesis of azo-POF-1: Tetrakis(4-nitrophenyl)methane (500 mg, 1 mmol) was dissolved in a mixture of 7 ml of THF and 8 ml of DMF. NaOH (640 mg, 16 mmol) in 1.5 ml de-ionized water and zinc powder (588 mg, 9 mmol) were added to the solution. The mixture was heated at 65 oC for 36 h and cooled to room temperature. The reaction mixture was poured into 100 ml 2M HCl and stirred for 1h. The yellow-orange solid was filtered off and washed with water, acetone and THF, followed by Soxhlet extraction from water (48 hours) and THF (48 hours). The yellow- orange solid was dried at 110 °C under vacuum for 8 hours to yield Azo-POF-1 in 78% yield. Anal. Calcd. For azo-POF-1: C, 80.63%; H, 4.33%; N, 15.04%. Found: C, 71.15%; H, 4.60%; N, 12.75%.
S6 N N N N O2N NO2
Zinc powder NaOH (aq.)
THF/DMF
N N N O2N NO2 N 3 azo-POF-2
Synthesis of azo-POF-2: 1,1,2,2-tetrakis(4-nitrophenyl)ethene (525 mg, 1 mmol) was dissolved in a mixture of 7 ml of THF and 8 ml of DMF. NaOH (640 mg, 16 mmol) in 1.5 ml de-ionized water and zinc powder (588 mg, 9 mmol) were added to the solution. The mixture was heated at 65 oC for 36 h and cooled to room temperature. The reaction mixture was poured into 100 ml 2M HCl and stirred for 1h. The yellow-orange solid was filtered off and washed with water, acetone and THF, followed by Soxhlet extraction from water (48 hours) and THF (48 hours). The yellow-orange solid was dried at 110 °C under vacuum for 8 hours to yield azo-POF-2 in 92% yield. Anal. Calcd. For azo-POF-2: C, 81.23%; H, 4.20%; N, 14.57%. Found: C, 69.62 %; H, 4.20%; N, 12.16%.
CH Br HC BF3K
K2CO3
Pd(PPh3)4 CH Br Br HC CH DMF HC
Br CH HC 6
ene-POF-1
Synthesis of ene-POF-1: Prepared by a known procedure.5 A two neck round bottom flask was charged with compound 6 (250 mg, 0.393 mmol), K2CO3 (651 mg, 4.72 mmol), potassium vinyltrifluoroborate (105 mg, 0.784 mmol) and 10 ml DMF. After the mixture was degassed with o Ar for 30 minutes, Pd(PPh3)4 (30 mg, 0.026 mmol) was added. The mixture was stirred at 80 C for 12 h and the temperature was raised to 120 oC. After kept at 120 oC for 60 h, the reaction was cooled to room temperature, and the solid was collected by filtration. The gray solid was washed with water, acetone and THF, followed by Soxhlet extraction from acetone for 24 h to obtain ene-POF-1 as a gray solid in quantitative yield.
S7 CH HC HC CH Br Br BF3K
K2CO3
Pd(PPh3)4
DMF
Br Br HC CH CH HC 7 ene-POF-2
Synthesis of ene-POF-2: Prepared by a known procedure.5 A two neck round bottom flask was charged with compound 7 (254 mg, 0.393 mmol), K2CO3 (651 mg, 4.72 mmol), potassium vinyltrifluoroborate (105 mg, 0.784 mmol) and 10 ml DMF. After the mixture was degassed with o Ar for 30 minutes, Pd(PPh3)4 (30 mg, 0.026 mmol) was added. The mixture was stirred at 80 C for 12 h and the temperature was raised to 120 oC. After kept at 120 oC for 60 h, the reaction was cooled to room temperature, and the solid was collected by filtration. The gray solid was washed with water, acetone and THF, followed by Soxhlet extraction from acetone for 24 h to obtain ene-POF-2 as a yellow solid in quantitative yield.
S8 3. FT-IR spectra
azo-POF-1
azo-POF-2
model compound 1
model compound 2
TNPM
TNPE 4000 3500 3000 2500 2000 1500 1000 Wavenumber (cm-1) Figure S1. FT-IR spectra of azo-POFs, model compounds, and related starting materials.
S9
azo-POF-1
azo-POF-2
model compound 1
model compound 2
TNPM
TNPE 2000 1500 1000 Wavenumber (cm-1) Figure S2. FT-IR spectra of azo-POFs, model compounds, and related starting materials (2000- 1000 cm-1).
S10
ene-POF-1
ene-POF-2
TBPM
TBPE
4000 3500 3000 2500 2000 1500 1000 Wavenumber (cm-1) Figure S3. FT-IR spectra of ene-POFs and related starting materials.
S11
ene-POF-1
ene-POF-2
TBPM
TBPE
2000 1500 1000 500 Wavenumber (cm-1) Figure S4. FT-IR spectra of ene-POFs and related starting materials (2000-500 cm-1).
S12 4. 13C NMR spectra
Model compound 1
200 180 160 140 120 100 80 60 40 20 0 Chemical shift (ppm)
Model compound 1
160 150 140 130 120 110 Chemical shift (ppm) Figure S5. 13C NMR spectra of model compound 1.
S13 Model compound 2
200 180 160 140 120 100 80 60 40 20 0 Chemical shift (ppm)
Model compound 2
160 150 140 130 120 110 Chemical shift (ppm) Figure S6. 13C NMR spectra of model compound 2.
S14
N N
N N n
Azo-POF-1
200 180 160 140 120 100 80 60 40 20 0 Chemical shift (ppm) Figure S7. Solid-state 13C CP-MAS NMR spectrum of azo-POF-1.
N N
N N n
Azo-POF-2
200 180 160 140 120 100 80 60 40 20 0 Chemical shift (ppm) Figure S8. Solid-state 13C CP-MAS NMR spectrum of azo-POF-2.
S15 5. Powder X-ray diffraction
Azo-POF-2
Azo-POF-1
10 20 30 40 50 60 70 80 2 Theta Figure S9. Powder X-ray diffraction patterns of azo-POFs
S16 6. Thermal gravimetric analysis of azo-POFs
100
80
60 ) % (
s
s 40 a M 20 azo-POF-1 azo-POF-2
0 100 200 300 400 500 600 700 800
Temperature (oC)
Figure S10. Thermal gravimetric analysis of azo-POFs
S17 7. Additional gas adsorption data for azo-POFs and ene-POFs
Gas adsorption measurements were performed using an ASAP 2020 volumetric adsorption analyzer using high-purity grade (99.999%) gases. N2 and gas adsorption isotherms were measured at 77 K using a liquid N2 bath; CO2 adsorption isotherms were measured at 273 K using an ice water bath and 291 K and 298 K using water bath. All samples were degassed at 150 °C for 5 h before gas measurements. Pore size distribution was calculated from N2 isotherms using a spherical/cylindrical pore NLDFT adsorption branch model.
The isosteric heats of adsorption were calculated using a virial type thermal equation given below based on the adsorption at 273 K and 291 K:
x y 1 i i ln(P)= ln(n)+ ai n + bi n T i=0 i=0 where the pressure (P) is expressed in mmHg, the amount absorbed (n) is expressed in mmol/g, and the temperature (T) is expressed in K. The virial coefficients ai and bi were fit by increasing the respective number of each (x and y) until a sufficient goodness of fit was reached. The values of the virial coefficients a0 to ax were than used to calculate the isosteric heat of adsorption (Qst) based on the equation given below:
x i Qst = -Rai n i=0
Henry’s law selectivities (SH) were calculated by the ratio of Henry’s law constants of CO2 (HC) and N2 (HN).
HC SH = HN
The Henry’s law constants for CO2 and N2 were obtained by the slope of linear fitting of the initial data (pressure less than 0.1 bar) of the gas adsorption isotherms.
Ideal absorbed solution theory (IAST) selectivities were calculated by fitting the single-site Langmuir model for N2 isotherms as given below:
q bP q = sat 1+ bP
and the dual-site Langmuir model for CO2 isotherms as given below:
S18 qsat ,1b1P qsat,2b2P q = q1 + q2 = + 1+ b1P 1+ b2P
where the pressure (P) is expressed in mmHg, the saturation loading (qsat) is expressed in mmol/g, the molar loading of adsorbate (q) is measured in mmol/g, and b is the fitted parameter for the isotherm. 1 and 2 refer to two different sites. The IAST selectivity factors (SIAST) were than calculated using the following equation:
qA / qB SIAST = PA / PB where qA and qB are the are amount of amounts of A and B absorbed respectively, and PA and PB are the partial pressure of A and B respectively.
S19 0.0008 azo-POF-1 0.0007 SA = 712 m2/g 0.0006 BET R2= 0.99975 ]
) 0.0005 1
-
P 0.0004 / 0 P ( 0.0003 Q
[ Equation y = a + b*x / Weight No Weighting 1 Residual Sum 6.05165E-11 0.0002 of Squares Pearson's r 0.9999 Adj. R-Square 0.99975 0.0001 Value Standard Error B Intercept 4.86333E-7 3.09694E-6 B Slope 0.00611 4.35568E-5 0.0000 0.00 0.02 0.04 0.06 0.08 0.10 0.12
P/P0
0.0012 azo-POF-2
0.0010 2 SABET= 439 m /g R2= 0.99942 ]
) 0.0008 1
-
P /
0 0.0006
P y = a + b*x ( Equation Weight No Weightin Q
[ Residual 2.08563E-1 / Sum of 0 1 0.0004 Squares Pearson's r 0.99978 Adj. R-Squar 0.99942 Value Standard Err 0.0002 D Intercept 3.47453E- 7.68785E-6 D Slope 0.00987 1.18953E-4 0.00 0.02 0.04 0.06 0.08 0.10 0.12
P/P0
Figure S11. BET surface area plots of azo-POFs based on N2 adsorption isotherms.
S20 0.0007 ene-POF-1
0.0006 2 SABET= 755 m /g 2 0.0005 R = 0.99996 ] ) 1
-
0.0004 P / 0 P ( 0.0003 Equation y = a + b*x
Q Weight No Weighting [
/ Residual Sum 6.10662E-12
1 of Squares 0.0002 Pearson's r 0.99999 Adj. R-Square 0.99996 Value Standard Erro F Intercept 1.20679E-5 1.07611E-6 0.0001 F Slope 0.00575 1.55006E-5
0.00 0.02 0.04 0.06 0.08 0.10 0.12
P/P0
0.0007 ene-POF-2
0.0006 2 SABET=622 m /g
] 2 ) 0.0005 R = 0.99999 1
-
P /
0 0.0004
P y = a + b*x ( Equation Weight No Weighting Q
[ Residual Sum 6.10407E-13 / 0.0003 of Squares 1 Pearson's r 1 Adj. R-Square 0.99999 0.0002 Value Standard Error H Intercept 2.00813E-5 4.73358E-7 H Slope 0.00698 7.91641E-6 0.0001 0.00 0.02 0.04 0.06 0.08 0.10 0.12
P/P0
Figure S12. BET surface area plots of ene-POFs based on N2 adsorption isotherms.
S21 70 azo-POF-1 N2 at 273 K 60 azo-POF-1 CO2 at 273 K 50 ) g / 3 40 m c (
e 30 k a t
p 20 U 10
0 0 200 400 600 800 Pressure (mmHg)
50 azo-POF-1 N2 at 298 K azo-POF-1 CO at 298 K 40 2 ) g
/ 30 3 m c (
e 20 k a t p U 10
0 0 200 400 600 800 Pressure (mmHg)
Figure S13. CO2 and N2 adsorption isotherms of azo-POF-1.
S22 45 azo-POF-2 N at 273 K 40 2 azo-POF-2 CO2 at 273 K 35 ) g
/ 30 3 m
c 25 (
n
o 20 i t p
r 15 o s
d 10 A 5 0 0 200 400 600 800 Pressure (mmHg)
30 azo-POF-2 N2 at 298 K
25 azo-POF-2 CO2 at 298 K ) g
/ 20 3 m c ( 15 n o i t p
r 10 o s d
A 5
0 0 200 400 600 800 Pressure (mmHg)
Figure S14. CO2 and N2 adsorption isotherms of azo-POF-2.
S23 45 ene-POF-1 N at 273 K 40 2 ene-POF-1 CO2 at 273 K 35 ) g
/ 30 3 m
c 25 (
n
o 20 i t p
r 15 o s
d 10 A 5 0 0 200 400 600 800 Pressure (mmHg)
25 ene-POF-1 N2 at 298 K ene-POF-1 CO at 298 K 20 2 ) g / 3 15 m c (
n o i
t 10 p r o s
d 5 A
0 0 200 400 600 800 Pressure (mmHg)
Figure S15. CO2 and N2 adsorption isotherms of ene-POF-1.
S24 40 ene-POF-2 N2 at 273 K 35 ene-POF-2 CO2 at 273 K 30 ) g / 3 25 m c ( 20 n o i t 15 p r o
s 10 d A 5 0 0 200 400 600 800 Pressure (mmHg)
25 ene-POF-2 N2 at 298 K ene-POF-2 CO at 298 K 20 2 ) g
/ 15 3 m c (
e 10 k a t p U 5
0 0 200 400 600 800 Pressure (mmHg)
Figure S16. CO2 and N2 adsorption isotherms of ene-POF-2.
S25 8
6
4 ) P ( azo-POF-1 n 2 l 273 K 291 K 0
-2 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
CO2 Uptake (mmol/g)
8
6
4
) 2 P ( azo-POF-2 n l 273 K 0 291 K -2
-4 0.0 0.5 1.0 1.5 2.0 2.5
CO2 Uptake (mmol/g)
Figure S17. Virial fitting for CO2 isotherms of azo-POFs
S26 8
6
4 ) P ( ene-POF-1 n
l 2 273 K 291 K 0
-2 0.0 0.5 1.0 1.5 2.0 2.5
CO2 Uptake (mmol/g)
8
6
4 ) P ( ene-POF-2 n
l 2 273 K 291 K 0
-2 0.0 0.5 1.0 1.5 2.0 2.5
CO2 Uptake (mmol/g)
Figure S18. Virial fitting for CO2 isotherms of ene-POFs
S27 50
40 )
l 30 o m / J k (
20 t s
Q azo-POF-1 10 azo-POF-2 ene-POF-1 ene-POF-2 0 0.00 0.25 0.50 0.75 1.00 1.25 Uptake (mmol/g)
Figure S19. Isosteric heats of adsorption for CO2.
S28 6 azo-POF-1 N2 at 273 K azo-POF-1 CO at 273 K 5 2
4 ) g / g
m 3 (
e Slope Intercept R square k 2
a CO 6.19E-01 2.45E-02 0.9993
t 2 2
p N 9.02E-03 -2.44E-03 0.9999 U 1
0 0 10 20 30 40 50 60 70 Pressure (mmHg)
2.0 azo-POF-1 N2 at 298 K
azo-POF-1 CO2 at 298 K 1.5 ) g / g
m 1.0 (
e Slope Intercept R square k CO2 2.35E-01 -8.83E-03 0.9999 a t N2 5.06E-03 6.93E-04 0.9999 p
U 0.5
0.0 0 10 20 30 40 50 60 70 Pressure (mmHg)
Figure S20. CO2/N2 initial slope selectivity studies for azo-POF-1.
S29 3.5 azo-POF-2 N2 at 273 K
3.0 azo-POF-2 CO2 at 273 K 2.5 ) g / 2.0 g m ( 1.5 Slope Intercept R square e
k CO2 3.95E-01 -6.11E-04 0.9997 a t N2 5.19E-03 1.86E-04 0.9999
p 1.0 U 0.5 0.0 0 10 20 30 40 50 60 70 Pressure (mmHg)
1.5 azo-POF-2 N2 at 298 K
azo-POF-2 CO2 at 298 K
1.0 ) g / g m (
e Slope Intercept R square k CO2 1.65E-01 -7.44E-03 0.9999 a
t 0.5 N2 3.03E-03 1.07E-03 0.9999 p U
0.0 0 10 20 30 40 50 60 70 Pressure (mmHg)
Figure S21. CO2/N2 initial slope selectivity studies for azo-POF-2.
S30 2.5 ene-POF-1 N2 at 273 K
ene-POF-1 CO2 at 273 K 2.0 ) g
/ 1.5 g m (
e Slope Intercept R square
k 1.0 2
a CO 2.74E-01 -5.25E-04 0.9998 t 2
p N 5.53E-03 -7.42E-04 0.9999 U 0.5
0.0 0 10 20 30 40 50 60 70 Pressure (mmHg)
1.00 ene-POF-1 N2 at 298 K
ene-POF-1 CO2 at 298 K 0.75 ) g / g m
( 0.50
e Slope Intercept R square
k CO2 1.07E-01 -3.91E-03 0.9999 a t N2 3.37E-03 -3.47E-04 0.9999 p
U 0.25
0.00 0 10 20 30 40 50 60 70 Pressure (mmHg)
Figure S22. CO2/N2 initial slope selectivity studies for ene-POF-1.
S31 2.0 ene-POF-2 N2 at 273 K
ene-POF-2 CO2 at 273 K 1.5 ) g / g
m 1.0 (
e Slope Intercept R square
k CO2 2.26E-01 2.10E-04 0.9998 a t N2 4.18E-03 -2.38E-04 0.9999 p
U 0.5
0.0 0 10 20 30 40 50 60 70 Pressure (mmHg)
0.75 ene-POF-2 N2 at 298 K
ene-POF-2 CO2 at 298 K
0.50 ) g / g m (
Slope Intercept R square e
k CO2 8.50E-02 -5.01E-03 0.9999 a
t 0.25 N2 2.45E-03 1.07E-03 0.9999 p U
0.00 0 10 20 30 40 50 60 70 Pressure (mmHg)
Figure S23. CO2/N2 initial slope selectivity studies for ene-POF-2.
S32 100 azo-POF-1 )
g 273 K m / 80 298 K g m (
y t i 60 v i t c e l
e 40 S
2 N / 2
O 20 C
T S A I 0 0 200 400 600 800 Pressure (mmHg)
100 azo-POF-2 )
g 273 K m / 80 298 K g m (
y t i 60 v i t c e l
e 40 S
2 N / 2
O 20 C
T S A I 0 0 200 400 600 800 Pressure (mmHg)
Figure S24. CO2/N2 IAST selectivity studies for azo-POFs for a molar ratio of 15:85.
S33 100 ene-POF-1 )
g 273 K m / 80 298 K g m (
y t i 60 v i t c e l
e 40 S
2 N / 2
O 20 C
T S A I 0 0 200 400 600 800 Pressure (mmHg)
100 ene-POF-2 )
g 273 K m / 80 298 K g m (
y t i 60 v i t c e l
e 40 S
2 N / 2
O 20 C
T S A I 0 0 200 400 600 800 Pressure (mmHg)
Figure S25. CO2/N2 IAST selectivity studies for ene-POFs for a molar ratio of 15:85.
S34 References
(1) Ganesan, P.; Yang, X.; Loos, J.; Savenije, T. J.; Abellon, R. D.; Zuilhof, H.; Sudholter, E. J. J. Am. Chem. Soc. 2005, 127, 14530. (2) Gorvin, J. H. J. Chem. Soc. 1959, 678. (3) Lu, W.; Yuan, D.; Zhao, D.; Schilling, C. I.; Plietzsch, O.; Muller, T.; Bräse, S.; Guenther, J.; Blümel, J.; Krishna, R.; Li, Z.; Zhou, H.-C. Chem. Mater. 2010, 22, 5964. (4) Xu, Y.; Chen, L.; Guo, Z.; Nagai, A.; Jiang, D. J. Am. Chem. Soc. 2011, 133, 17622. (5) Sun, L.; Zou, Y.; Liang. Z.; Yu. J.; Xu, R. Poly. Chem. 2014, 5, 471.
S35