Supporting Information: O-Farha@northwestern - Edu

SUPPORTING INFORMATION
Opening Up ZIF-8: A Catalytically Active Zeolitic Imidazolate

Framework Of Sodalite Topology With Unsubstituted Linkers
Olga Karagiaridia, Marianne B. Lalondea, Wojciech Burya,b, Amy A. Sarjeanta, Omar K.
Farhaa* and Joseph T. Huppa*
a
Department of Chemistry and International Institute for Nanotechnology, Northwestern
University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
b
Department of Chemistry, Warsaw University of Technology, Noakowskiego 3,
Warsaw, Poland 00-664
*To whom correspondence should be addressed. E-mail: j-hupp@u.northwestern.edu, o-

farha@northwestern.edu
Telephone: (847)-491-3504. Fax: (847)-467-1425.
S1
Section Page
S1. 1H NMR Measurements S3
S2. PXRD Measurements S5
S3. Chemical Stability S7
S4. Reverse SALE Experiment S8
S5. Nitrogen Sorption Measurements S9
S6. TGA-MS Data S11
S7. Crystallographic Information Data S13
S2
Section S1. 1H NMR measurements
im
SALEM-2
mim
im mim
mim mim
ZIF-8 DMF
DMF
Figure S1. 1H NMR spectrum of SALEM-2 (7 days into the reaction) and ZIF-8.
Figure S2. 1H NMR spectra of ZIF-8 as it is transformed to SALEM-2 over the course
of 7 days of the SALE reaction. The peaks whose intensities were used to calculate the
percent conversion to SALEM-2 are boxed.
S3
100
90
80
% exchange to im
70
60
50
40
30
20
10
0
0 1 2 3 4 5 6 7
Time [days]
Figure S3. Progress of the SALE reaction expressed as percent exchange from mim to
im.
Table S1. NMR peak intensities (relative to CHa im)
Time Conversion
CHa im CHb im CH mim CH3 mim
[days] [%]
1 1.00 0.47 6.10 9.23 14
2 1.00 0.49 1.68 2.55 37
3 1.00 0.49 0.36 0.55 73
4 1.00 0.49 0.21 0.30 83
5 1.00 0.49 0.24 0.35 81
6 1.00 0.49 0.16 0.23 86
7 1.00 0.49 0.15 0.22 87
S4
Section S2. PXRD measurements
SALEM-2 (n-BuOH)
SALEM-2 (DMF)
ZIF-8
5 7 9 11 13 15 17 19
2θ
Figure S4. PXRD patterns for ZIF-8 and the products after performing SALE in DMF
and n-BuOH. SALE in n-BuOH yields crystalline SALEM-2 of same topology as ZIF-8,
whereas SALE in DMF leads to loss of crystallinity.
S5
PXRD: SALEM-2 Before and After Catalysis
SALEM-2 as synthesized
SALEM-2 after catalysis
Intensity
5 10 15 20
Figure S5: PXRD patterns of: SALEM-2 as synthesized (top), SALEM-2 after use as a
Brønsted-base catalyst (bottom).
S6
Section S3. Chemical Stability
Figure S6. PXRD patterns of ZIF-8, unactivated SALEM-2 and SALEM-2 following
immersion in boiling H2O for 24 hours.
S7
Section S4. Reverse SALE Experiment
Figure S7. 1H NMR spectrum of SALEM-2 following solution exposure to excess Hmim
under SALE conditions. The integration indicates back-exchange of ~79% of the
im to mim to yield a ZIF of approximate composition Zn(im)0.4(mim)1.6.
S8
reverse SALEM-2 ZIF-8
5 7 9 11 13 15 17 19
2θ
Figure S8. PXRD pattern of the products of the reverse SALE reaction. The SOD
topology is preserved.
Section S5. Nitrogen sorption measurements
Figure S9. Nitrogen gas sorption isotherm at 77 K for SALEM-2.
S9
350
y = 5204.2x + 22.575
R² = 0.99855
300
250
P/[V(Po-P)]
200
150
100
50
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
P/Po
Figure S10. BET surface area plot for SALEM-2 for P/Po 0.005-0.05. The BET surface
area calculated from this P/Po is 830 m2/g.
Figure S11. Nitrogen gas sorption isotherm at 77 K for ZIF-8.
S10
250
y = 4024.7x + 3.575
R² = 0.99953
200
P/[V(Po-P)]
150
100
50
0
0 0.01 0.02 0.03 0.04 0.05 0.06
P/Po
Figure S12. BET surface area plot for ZIF-8 for P/Po 0.005-0.05. The BET surface area
calculated from this P/Po is 1080 m2/g.
Section S6. TGA-MS data
100
90
80
weight change [%]
70
60
50
40
30
25 125 225 325 425 525 625 725
Temperature [ºC]
Figure S13. TGA curve for SALEM-2. SALEM-2 appears to be thermally sable to
~400 ºC.
S11
Table S2. MS data for ZIF-8 and SALEM-2 soaked in n-hexane, cyclohexane and
toluene.
Tmax of the MS
Sample m/z peaks observed
signal [ºC]
ZIF-8 in n-hexane 41, 42, 43, 56, 57, 86 155
SALEM-2 in n-hexane 41, 42, 43, 56, 57, 86 108
ZIF-8 in cyclohexane N/A N/A
SALEM-2 in cyclohexane 41, 56, 69, 84 160
ZIF-8 in toluene N/A N/A
SALEM-2 in toluene 91. 92 130
S12
Section S7. Crystallographic information data
Table S3. Crystal data and structure refinement for SALEM-2 (100% im)
Empirical formula C6 H6 N4 Zn
Formula weight 199.52
Temperature 100 K
Wavelength 1.54184 Å
Crystal system Cubic
Space group I-43m
Unit cell dimensions a = b = c = 16.8303 (2) Å
α = β = γ = 90º
Volume 4767.33 (10) Å3
Z 12
Density (calculated) 0.834 Mg m-3
Absorption coefficient 1.89 mm-1
F(000) 1200
Crystal size 0.18 x 0.16 x 0.06 mm
Theta range for data collection 3.7º - 66.4º
Index ranges -20 ≤ h ≤ 19
-10 ≤ k ≤ 19
-19 ≤ l ≤ 17
Reflections collected 10526
Independent reflections 822 [Rint = 0.0745]
Refinement method Full-matrix least-squares on F2
Reflections/restraints/parameters 822/7/37
Goodness of fit on F2 1.10
Final R indices R[F2 > 2σ(F2)] = 0.027, wR(F2) = 0.070
Largest diff. peak and hole 0.30, -0.17
S13
Table S4. Crystal data and structure refinement for SALEM-2 (fitted to 85% im)
Empirical formula C6.30 H6.60 N4 Zn

Formula weight 203.73
Temperature 100 K
Wavelength 1.54184 Å
Crystal system Cubic
Space group I-43m
Unit cell dimensions a = b = c = 16.8303 (2) Å
α = β = γ = 90º
Volume 4767.33 (10) Å3
Z 12
Density (calculated) 0.852 Mg m-3
Absorption coefficient 1.90 mm-1
F(000) 1229
Crystal size 0.18 x 0.16 x 0.06 mm
Theta range for data collection 3.7º - 66.4º
Index ranges -20 ≤ h ≤ 19
-10 ≤ k ≤ 19
-19 ≤ l ≤ 17
Reflections collected 10526
Independent reflections 822 [Rint = 0.027]
Refinement method Full-matrix least-squares on F2
Reflections/restraints/parameters 822/8/43
Goodness of fit on F2 1.12
Final R indices R[F2 > 2σ(F2)] = 0.026, wR(F2) = 0.062
Largest diff. peak and hole 0.30, -0.17
S14

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SUPPORTING INFORMATION

Opening Up ZIF-8: A Catalytically Active Zeolitic Imidazolate

*To whom correspondence should be addressed. E-mail: j-hupp@u.northwestern.edu, o-

Telephone: (847)-491-3504. Fax: (847)-467-1425.

S2. PXRD Measurements S5

S3. Chemical Stability S7

S4. Reverse SALE Experiment S8

S5. Nitrogen Sorption Measurements S9

S6. TGA-MS Data S11

S7. Crystallographic Information Data S13

Table S1. NMR peak intensities (relative to CHa im)

Section S5. Nitrogen sorption measurements

Figure S9. Nitrogen gas sorption isotherm at 77 K for SALEM-2.

Figure S11. Nitrogen gas sorption isotherm at 77 K for ZIF-8.

Section S6. TGA-MS data

Empirical formula C6.30 H6.60 N4 Zn

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