Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
This journal is © the Partner Organisations 2017
A Comparative Study of the Effect of Functional Groups on C2H2
Adsorption in NbO-Type Metal-Organic Frameworks
Fengli Chen, Dongjie Bai, Xia Wang and Yabing He*
College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004,
China. E-mail: [email protected]
Synthesis of 5,5’-(1-aminebenzene-2,5-diyl) diisophthalic aicd (H4L1)
To a 250-mL single-neck round-bottom flask equipped with a condenser and a
magnetic stirring bar was added 2,5-dibromobenzenamine (1.00 g, 3.98 mmol),
dimethyl 5-(pinacolbory)isophthalate (2.81 g, 8.78 mmol), Cs2CO3 (3.89 g, 11.94
mmol) and Pd(PPh3)4 (0.23 g, 0.20 mmol). The flask was evacuated and then
back-filled with nitrogen. After the process was repeated three times, dry dioxane (50
mL) was added via syringe. The resulting suspension was stirred under reflux for 72 h.
After the reaction mixture was allowed to cool to room temperature, the solvents were
removed, and CH2Cl2 (100 mL) and H2O (100 mL) were added. The mixture was
filtered. The organic phase was separated and the aqueous phase was extracted with
CH2Cl2 (3 × 50 mL). The combined organic phase was washed with brine (50 mL),
dried over anhydrous MgSO4, filtered and evaporated under reduced pressure.
Recrystallization of the residue from toluene afforded the tetramethyl ester
intermediate in 23% yield (0.44 g, 0.92 mmol).
To a solution of the tetramethyl intermediate (0.44 g, 0.92 mmol) in THF (40 mL)
and MeOH (40 mL) was added 6 M NaOH (40 mL, 240 mM). The resulting mixture
was stirred at 60 oC for 12 h. After the removal of the solvents, the residue was
dissolved in water, and acidified with conc. HCl under an ice-water bath. The
precipitation was collected by filtration, and dried in a vacuum at 70 oC to afford the
target compound in a quantitative yield.
Synthesis of 5,5’-(1-methylbenzene-2,5-diyl) diisophthalic aicd (H4L2)
To a 250-mL single-neck round-bottom flask equipped with a condenser and a
magnetic stirring bar was added 1,4-dibromo-2-methylbenzene (1.00 g, 4.00 mmol),
dimethyl 5-(pinacolbory)isophthalate (2.82 g, 8.80 mmol), Cs2CO3 (3.91 g, 12.00
mmol) and Pd(PPh3)4 (0.23 g, 0.20 mmol) . The flask was evacuated and back-filled
back with nitrogen. After the process was repeated three times, dry dioxane (50 mL)
was added via syringe. The resulting suspension was stirred under reflux for 72 h.
After the reaction mixture was allowed to cool to room temperature, the solvents were
removed under reduced pressure, and CH2Cl2 (100 mL) and H2O (100 mL) were
added. The mixture was filtered. The organic phase was separated and the aqueous
phase was extracted with CH2Cl2 (3 × 50 mL). The combined organic phase was
washed with brine (50 mL), dried over anhydrous MgSO4 and filtered. Volatiles were
removed by rota-evaporation under reduced pressure and recrystallization of the
residue from toluene afforded the tetramethyl ester intermediate in 17% yield (0.32 g,
0.67 mmol).
To a suspension of the tetramethyl intermediate (0.32 g, 0.67 mmol) in THF (30 mL)
and MeOH (30 mL) was added 6 M NaOH (30 mL, 180 mM). The resulting mixture
was heated at 80 oC overnight with stirring. After the removal of the solvents, the
residue was dissolved in water, and acidified with conc. HCl under an ice-water bath.
The precipitation was collected by filtration, and dried in a vacuum at 70 oC to afford
the target compound in a quantitative yield.
Synthesis of 5,5’-(1-nitrobenzene-2,5-diyl) diisophthalic aicd (H4L3)
To a 250-mL single-neck round-bottom flask equipped with a condenser and a
magnetic stirring bar was added 1,4-dibromo-2-nitrobenzene (1.00 g, 3.56 mmol),
dimethyl 5-(pinacolbory)isophthalate (2.51 g, 7.84 mmol), Cs2CO3 (3.48 g, 10.68
mmol) and Pd(PPh3)4 (0.20 g, 0.17 mmol). The flask was evacuated and then
back-filled with nitrogen. After the process was repeated three times, dry dioxane (50
mL) was added via syringe. The resulting suspension was stirred under reflux for 72 h.
After the reaction mixture was allowed to cool to room temperature, the solvents were
removed, and CH2Cl2 (100 mL) and H2O (100 mL) were added. The mixture was
filtered. The organic phase was separated and the aqueous phase was extracted with
CH2Cl2 (3 × 50 mL). The combined organic phase was washed with brine (50 mL),
dried over anhydrous MgSO4 and filtered. Volatiles were removed by rota-evaporation
under reduced pressure and the residue was purified by silica gel column
chromatography with petroleum ether/dichloromethane/ethyl acetate (10/1/1, v/v/v) as
eluent, affording the tetramethyl ester intermediate in 17% yield (0.31 g, 0.61 mmol).
To a suspension of the tetramethyl intermediate (0.31 g, 0.61 mmol) in THF (30 mL)
and MeOH (30 mL) was added 6 M NaOH (30 mL, 180 mM). The resulting mixture
was heated at 40 oC for 12 h. After the removal of the solvents, the residue was
dissolved in water, and acidified with conc. HCl under an ice-water bath. The
precipitation was collected by filtration, and dried in a vacuum at 70 oC to afford the
target compound in a quantitative yield.
Synthesis of 5,5’-(1-fluorobenzene-2,5-diyl) diisophthalic aicd (H4L4)
To a 250-mL single-neck round-bottom flask equipped with a condenser and a
magnetic stirring bar was added 1,4-dibromo-2-fluorobenzene (1.00 g, 3.94 mmol),
dimethyl 5-(pinacolbory)isophthalate (2.77 g, 8.65 mmol), Cs2CO3 (3.85 g, 11.82
mmol) and Pd(PPh3)4 (0.23 g, 0.20 mmol). The flask was evacuated and then
back-filled back with nitrogen. After the process was repeated three times, dry
dioxane (50 mL) was added via syringe. The resulting suspension was stirred under
reflux for 72 h. After the reaction mixture was allowed to cool to room temperature,
the solvents were removed, and CH2Cl2 (100 mL) and H2O (100 mL) were added. The
mixture was filtered. The organic phase was separated and the aqueous phase was
extracted with CH2Cl2 (3 × 50 mL). The combined organic phase was washed with
brine (50 mL), dried over anhydrous MgSO4 and filtered. Volatiles were removed by
rota-evaporation under reduced pressure and the recrystallization of the residue from
toluene afforded the tetramethyl ester intermediate in 22% yield (0.41 g, 0.85 mmol).
To a suspension of the tetramethyl intermediate (0.41 g, 0.85 mmol) in THF (40 mL)
and MeOH (40 mL) was added 6 M NaOH (40 mL, 240 mM). The resulting mixture
was heated at 70 oC overnight. After the removal of the solvents, the residue was
dissolved in water, and acidified with conc. HCl under an ice-water bath. The
precipitation was collected by filtration, and dried in a vacuum at 70 oC to afford the
target compound in a quantitative yield.
Synthesis of 5,5’-(1-trifluoromethylbenzene-2,5-diyl) diisophthalic aicd (H4L5)
To a 250-mL single-neck round-bottom flask equipped with a condenser and a
magnetic stirring bar was added 1,4-dibromo-2-(trifluoromethyl)benzene (1.00 g, 3.29
mmol), dimethyl 5-(pinacolbory)isophthalate (2.32 g, 7.25 mmol), Cs2CO3 (3.22 g,
9.88 mmol) and Pd(PPh3)4 (0.19 g, 0.16 mmol). The flask was evacuated and then
back-filled with nitrogen. After the process was repeated three times, dry dioxane (50
mL) was added via syringe. The resulting suspension was stirred under reflux for 72 h.
After the reaction mixture was allowed to cool to room temperature, the solvents were
reduced, and CH2Cl2 (100 mL) and H2O (100 mL) were added. The mixture was
filtered the organic phase was separated and the aqueous phase was extracted with
CH2Cl2 (3 × 50 mL). The combined organic phase was washed with brine (50 mL),
dried over anhydrous MgSO4 and filtered. Volatiles were removed by rota-vaporation
under reduced pressure, and the residue was purified by silica gel column
chromatography with petroleum ether/dichloromethane/ethyl acetate (5:1:1, v/v/v) as
eluent, affording the tetramethyl ester intermediate in 12% yield (0.21 g, 0.40 mmol).
To a suspension of the tetramethyl intermediate (0.21 g, 0.40 mmol) in THF (20 mL)
and MeOH (20 mL) was added 6 M NaOH (20 mL, 120 mM). The resulting mixture
was heated at 70 oC overnight. After the removal of the solvents, the residue was
dissolved in water, and acidified with conc. HCl under an ice-water bath. The
precipitation was collected by filtration, and dried in a vacuum at 70 oC to afford the
target compound in a quantitative yield.
Fig. S1 Comparison of the as-synthesized and simulated PXRD patterns for ZJNU-34
(a), ZJNU-35 (b), ZJNU-36 (c), ZJNU-37 (d) and ZJNU-38 (e).
Fig. S2 TGA curves of the as-synthesized ZJNU-34 (a), ZJNU-35 (b), ZJNU-36 (c),
ZJNU-37 (d), ZJNU-38 (e) and NOTT-101 (f).
Fig. S3 Comparison of FTIR spectra of the organic ligands and the corresponding
MOF compounds.
Fig. S4 Comparison of cage structures in five MOF compounds investigated.
SBET = 1/(2.59786×10-7 + 0.00177)/22414×6.023×1023×0.162×10-18 = 2459 m2 g-1
SLangmuir = (1/0.00161)/22414×6.023×1023×0.162×10-18 = 2704 m2 g-1
Fig. S5 BET (a) and Langmuir (b) plots for ZJNU-34(NH2)
SBET =1/(2.56412×10-7+0.00168)/22414×6.023×1023×0.162×10-18 = 2591 m2 g-1
SLangmuir = (1/0.00154)/22414×6.023×1023×0.162×10-18 = 2827 m2 g-1
Fig. S6 BET (a) and Langmuir (b) plots for ZJNU-35(CH3)
SBET = 1/(2.16284×10-7+0.00183)/22414×6.023×1023×0.162×10-18 = 2379 m2 g-1
SLangmuir = (1/0.00165)/22414×6.023×1023×0.162×10-18 = 2638 m2 g-1
Fig. S7 BET (a) and Langmuir (b) plots for ZJNU-36(NO2)
SBET = 1/( 1.87659×10-7+ 0.0016)/22414×6.023×1023×0.162×10-18 = 2720 m2 g-1
SLangmuir = (1/ 0.00149)/22414×6.023×1023×0.162×10-18 = 2922 m2 g-1
Fig. S8 BET (a) and Langmuir (b) plots for ZJNU-37(F)
SBET = 1/( 4.8368×10-7+ 0.0019)/22414×6.023×1023×0.162×10-18 = 2291 m2 g-1
SLangmuir = (1/0.00173)/22414×6.023×1023×0.162×10-18 = 2516 m2 g-1
Fig. S9 BET (a) and Langmuir (b) plots for ZJNU-38(CF3)
SBET =1/(1.28013×10-7+0.00158)22414×6.023×1023×0.162×10-18 = 2755 m2 g-1
SLangmuir =(1/0.00147)/22414×6.023×1023×0.162×10-18 = 2961 m2 g-1
Fig. S10 BET (a) and Langmuir (b) plots for NOTT-101
Fig. S11 Low-pressure CH4 isotherms at four different temperatures for ZJNU-34 (a),
ZJNU-35 (b), ZJNU-36 (c), ZJNU-37 (d), ZJNU-38 (e) and NOTT-101 (f).
Fig. S12 Comparison of the pure-component isotherm data with the fitted isotherms
(shown by continuous solid lines).
Fig. S13. Comparison of C2H2/CH4 adsorption selectivity
8.13
3.01
7.0
8.00
7.88
7.75
6.0
7.63
7.50
7.435
7.50
7.0
6.0
5.0
5.0
4.0
HOOC
HOOC
4.0
3.0
2.0
3.0
2.357
2.512
8.0
7.448
7.695
7.693
9.0
1.07
8.25
10.0
7.708
11.0
7.771
12.0
1.06
8.0
8.139
8.136
8.456
8.454
8.491
8.456
8.454
8.139
8.136
7.771
7.708
7.695
7.693
7.448
7.435
8.00
1.09
1.10
1.08
8.506
HOOC
1.09
8.50
ppm
1.07
8.38
1.10
1.08
13.0
1.07
1.06
1.07
2.07
2.02
1.04
1.00
ppm
8.50
2.07
2.02
1.04
1.00
8.63
ppm
2.04
2.03
2.08
4.00
14.0
ppm
2.04
2.03
2.08
8.506
8.491
HOOC
COOH
NH2
COOH
7.00
1.0
COOH
CH3
7.38
COOH
2.506
3.394
7.104
7.084
7.268
7.229
7.210
8.462
8.448
8.407
8.244
13.377
3.00
1.97
8.50
3.00
7.0
6.0
7.732
7.742
7.774
8.305
8.409
8.509
2.508
7.742
7.732
7.774
8.305
8.409
8.50
1.08
7.0
2.00
8.0
1.06
1.00
9.0
ppm
1.08
1.99
1.99
8.0
2.00
1.06
1.97
1.99
1.99
ppm
2.08
2.00
1.00
2.08
2.00
8.509
HOOC
HOOC
6.0
5.0
5.0
COOH
NO2
COOH
ppm
8.00
4.0
4.0
3.0
HOOC
HOOC
ppm
8.00
3.0
2.0
COOH
F
COOH
2.512
2.507
2.503
2.498
2.091
7.721
7.701
8.010
8.007
8.359
8.354
8.149
8.145
8.129
8.124
8.419
8.416
8.534
8.531
8.511
8.507
2.515
2.512
2.509
3.371
7.653
7.666
8.188
8.179
8.166
8.139
7.666
7.653
8.139
8.166
8.179
8.188
8.537
8.507
8.505
8.557
8.557
8.537
8.507
8.505
13.520
HOOC
COOH
CF3
1.00
1.91
1.02
0.94
1.97
0.99
0.95
HOOC
8.60
ppm
8.50
8.40
8.30
8.20
8.10
8.00
11.0
10.0
9.0
7.70
COOH
7.60
8.0
7.0
6.0
5.0
4.0
3.0
2.0
13.20
12.674
4.02
4.02
2.00
13.30
13.208
13.205
13.248
7.262
12.674
13.208
13.205
13.248
12.0
7.80
1.00
13.0
1.91
1.02
0.94
1.97
0.99
0.95
4.00
14.0
ppm
7.90
13.10
13.00
12.90
12.80
12.70
12.60
HOOC
COOH
HOOC
COOH
12.50
ppm
4.02
4.02
2.00
13.0
12.0
ppm
Fig. S14 1H NMR spectra
11.0
10.0
9.0
8.0
7.0
Table S1 Crystal data and structure refinement for ZJNU-34-38.
MOFs
ZJNU-34(NH2)
ZJNU-35(CH3)
ZJNU-36(NO2)
ZJNU-37(F)
Empirical formula
C22H15Cu2NO10
C23H16Cu2O10
C22H13Cu2NO12
C22H13Cu2FO10
ZJNU-38(CF3)
C23 H13 Cu2 F3
O10
Formula weight
580.43
579.44
610.43
583.40
633.41
Temperature (K)
293(2)
293(2)
293(2)
293(2)
293(2)
Wavelength (Å)
1.54184
0.71073
0.71069
0.71073
0.71073
Crystal system
Trigonal
Trigonal
Trigonal
Trigonal
Trigonal
Space group
R-3m
R-3m
R-3m
R-3m
R-3m
a = 18.6153(7) Å
a = 18.6166(7) Å
a = 18.555(3) Å
a = 18.7065(19) Å
a = 18.5503(6) Å
b = 18.6153(7) Å
b = 18.6166(7) Å
b = 18.555(3) A
b = 18.7065(19) Å
b = 18.5503(6) A
c = 38.3750(13) Å
c = 38.6451(14) Å
c = 38.688(6) A
c = 38.488(3) Å
c = 38.8068(12) A
α = 90
α = 90
α = 90
α = 90
o
α = 90o
Unit cell dimensions
o
o
o
β = 90o.
β = 90o
β = 90o
β = 90o
β = 90o
γ = 120o
γ = 120o
γ = 120o
γ = 120o
γ = 120o
Volume (Å3)
11516.5(7)
11599.1(7)
11535(3)
11663.8(19)
11564.9(6)
Z
9
9
9
9
9
Dc (g cm )
0.753
0.747
0.791
0.748
0.819
μ (mm )
1.261
0.850
0.861
0.849
0.865
F(000)
2628
2628
2753
2628
2844
0.25 × 0.18 × 0.13
0.20 × 0.18 × 0.16
0.22 × 0.14 × 0.10
0.26 × 0.21 × 0.12
0.22 × 0.18 × 0.12
3.46 to 73.91
1.37 to 25.01
1.37 to 27.58 deg.
1.36 to 25.02
1.37 to 25.02
-23 ≤ h ≤ 20
-22 ≤ h ≤ 22
-24 ≤ h ≤ 24,
-22 ≤ h ≤ 22
-22 ≤ h ≤ 22
-22 ≤ k ≤ 19
-22 ≤ k ≤ 22
-24 ≤ k ≤ 24,
-22 ≤ k ≤ 22
-22 ≤ k ≤ 22
-46 ≤ l ≤ 32
-45 ≤ l ≤ 45
-50 ≤ l ≤ 47
-45 ≤ l ≤ 45
-46 ≤ l ≤ 46
Reflections collected / unique
14559 / 2816
65985 / 2512
77586 / 3259
66423 / 2523
66045 / 2506
Rint
0.0277
0.1541
0.1629
0.2139
0.1244
Completeness
98.6 %
100.0 %
100.0%
100.0 %
100.0 %
Max. and min. transmission
0.8532 and 0.7433
0.8759 and 0.8483
0.9189 and 0.8332
0.9050 and 0.8095
0.9033 and 0.8325
Data/restraints/parameters
2816 / 1 / 103
2512 / 18 / 92
3259 / 0 / 121
2523 / 0 / 103
2506 / 25 / 116
1.130
1.090
1.073
1.152
1.204
R1 = 0.0501,
R1 = 0.0577
R1 = 0.0631
R1 = 0.0528
R1 = 0.0557
wR2 = 0.1762
wR2 = 0.1814
wR2 = 0.1580
wR2 = 0.1506
wR2 = 0.1476
R1 = 0.0538,
R1 = 0.0832
R1 = 0.0997
R1 = 0.0814
R1 = 0.0720
wR2 = 0.1806
wR2 = 0.1926
wR2 = 0.1759
wR2 = 0.1564
wR2 = 0.1604
Largest diff. peak and hole (e.Å )
1.086 and -0.378
0.727 and -0.525
0.424 and -0.798
0.722 and -0.564
0.719 and -0.547
CCDC
1529129
1529132
1529130
1529131
1529128
-3
-1
Crystal size (mm)
θ range for data collection ( )
o
Limiting indices
2
Goodness-of-fit on F
Final R indices [I > 2σ(I)]
R indices (all data)
-3
Table S2 Langmuir-Freundich parameters for adsorption of C2H2 and CH4 in
ZJNU-34(NH2)
qsat
(mmol g-1)
b0
(kPa)-v
E
(kJ mol-1)
v
C2H2
27.75156
1.17624×10-5
18.208
0.6891
CH4
12.92465
1.42418×10-6
15.577
1
Table S3. Langmuir-Freundich parameters for adsorption of C2H2 and CH4 in
ZJNU-35(CH3)
qsat
(mmol g-1)
b0
(kPa)-v
E
(kJ mol-1)
v
C2H2
40.53896
1.52868×10-5
16.663
0.6345
CH4
12.23696
1.21437×10-6
15.920
1
Table S4 Langmuir-Freundich parameters for adsorption of C2H2 and CH4 in
ZJNU-36(NO2)
qsat
(mmol g-1)
b0
(kPa)-v
E
(kJ mol-1)
v
C2H2
51.75956
1.78909×10-5
16.151
0.57666
CH4
15.92367
1.32598×10-6
15.053
1
Table S5 Langmuir-Freundich parameters for adsorption of C2H2 and CH4 in
ZJNU-37(F)
qsat
(mmol g-1)
b0
(kPa)-v
E
(kJ mol-1)
v
C2H2
82.26879
1.43447×10-5
15.182
0.5883
CH4
13.31489
1.07866×10-6
15.814
1
Table S6 Langmuir-Freundich parameters for adsorption of C2H2 and CH4 in
ZJNU-38(CF3)
qsat
(mmol g-1)
b0
(kPa)-v
E
(kJ mol-1)
v
C2H2
63.28469
3.17191×10-5
14.048
0.55378
CH4
17.62945
9.99285×10-7
15.017
1
Table S7 Langmuir-Freundich parameters for adsorption of C2H2 and CH4 in
NOTT-101
qsat
(mmol g-1)
b0
(kPa)-v
E
(kJ mol-1)
v
C2H2
59.19957
1.48802×10-5
15.787
0.61397
CH4
13.39522
3.93239×10-6
12.785
1