Banerjee2008 SI

www.sciencemag.
org/cgi/content/full/319/5865/939/DC1
Supporting Online Material for

High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and
Application to CO2 Capture
Rahul Banerjee,* Anh Phan, Bo Wang, Carolyn Knobler, Hiroyasu Furukawa,
Michael O’Keeffe, Omar M. Yaghi*
*To whom correspondence should be addressed.

E-mail: rahul@chem.ucla.edu (R.B.); yaghi@chem.ucla.edu (O.M.Y.)
Published 15 February 2008, Science 319, 939 (2008)
DOI: 10.1126/science.1152516
This PDF file includes:
SOM Text S1 to S5
Figs. S1 to S86
Tables S1 to S23
Materials and Methods (160 pages) for:
High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and

Application to CO2 Capture
Rahul Banerjee1*, Anh Phan1, Bo Wang1, Carolyn Knobler1, Hiroyasu Furukawa1,
Michael O’Keeffe2, Omar M. Yaghi1*
1
Center for Reticular Chemistry at California NanoSystems Institute, Department
of Chemistry and Biochemistry, University of California, Los Angeles, 607 East
Charles E. Young Drive, Los Angeles, California 90095, USA. 2Department of
Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287,
USA. * E-Mail: rahul@chem.ucla.edu or yaghi@chem.ucla.edu
Table of Contents
Detailed synthesis procedures for ZIFs including multi-gram scale

Section S1. products, and experimental and simulated PXRD patterns. Elemental
microanalysis for ZIF-60, 61, 68 to 70, 74 and 76.
Representative optical photographs of ZIFs crystals (0.1 to 1 mm) and

Section S2. single crystal x-ray diffraction data collection, structure solution and
refinement procedures.
Thermal stability of ZIFs and the thermal gravimetric analysis (TGA)

Section S3.
data.
Chemical stability of ZIFs in refluxing organic and aqueous media and

Section S4.
the corresponding PXRD patterns.
Porosity of ZIFs and carbon dioxide (CO2) selectivity and capacity

Section S5.
studies.
1
Section S1: Detailed synthesis procedures for ZIFs including multi-gram scale
products, and experimental and simulated PXRD patterns. Elemental microanalyses
for ZIF-60, 61, 68 to 70, 74 and 76.
General Synthetic Procedures: Benzimidazole, 2-methylimidazole, 2-ethylimidazole,
5-chloro benzimidazole, purine and cobalt nitrate hexahydrate were purchased from the
Aldrich Chemical Co. and imidazole, N,N-dimethylformamide (DMF), N-
methylpyrrolidinone (NMP) were purchased from the Fisher Scientific International Inc.
2-nitroimidazole was purchased from 3B Scientific Corporation. N,N-diethylformamide
(DEF) was obtained from BASF Corporation. Zinc nitrate tetrahydrate was purchased
from EM Science. All starting materials were used without further purification. All
experimental operations were performed in air.
The fully integrated high throughput synthetic apparatus consists of a number of
components, including experimental design and execution software, robotic dispensing
and handling hardware, an automated high speed optical microscope for visualizing the
crystals/materials inside the wells, and the x-ray diffractometer for the data analysis and
structural interpretation. All ZIFs were synthesized by using this combinatorial
experimentation utilizing a 96-well glass plate as the reaction vessel. This design allows
us to use 0.300 mL reactant volume per well. A solution of imidazole(s) in DMF/DEF
(0.075–0.20 M) and a solution of a hydrated metal salt (usually nitrate) in DMF/DEF
(0.075–0.20 M) were used as stock solutions. This concentration range is used to avoid
contamination between two sets of reactions and to avoid blockage of the liquid handler
2
by precipitation of the reactant. DMF and DEF have been chosen as the solvents of
synthesis due to their high boiling points, which are suitable for the solvothermal
synthesis. A lower boiling solvent may result in the precipitation of the reactants rather
than of the product. After the 96-well glass plate was loaded with mixtures of stock
solutions dispensed by a programmed liquid handler (Gilson, model 215), it was covered
with a PTFE (poly tetrafluroethylene) sheet, sealed by fastening the sheet with a metal
clamp, then heated in an oven and allowed to react solvothermally for 24–96 h. Highly
crystalline materials were obtained by combining the requisite hydrated metal salt and
imidazole-type linkers. The very smooth interior of these 96 well glass-plates helps to
form diffraction quality single crystals. After reaction, the products were examined under
an automated optical microscope, isolated, and characterized by single-crystal x-ray
diffraction. The isolation of the sample array is accomplished in parallel by sonication
and transfer in a custom-designed shallow metal plate which allows the presence of small
a amount of solvent during the PXRD data collection. Samples were analyzed by a
Bruker D8 DISCOVER high throughput PXRD machine with a horizontal x-y stage for
automated analysis and equipped with an image plate detector system. The data
collection mode is in transmission geometry. The data collection time was 3–6 min per
sample. A structure database was set up that contains the simulated PXRD patterns of all
reported ZIFs. When a PXRD pattern of a new ZIF has been collected it can be checked
with this database in order to determine whether, if the material under study is a new
phase or it falls in the category of the ZIFs published already.
3
Thus far, ZIF-62, 64, 65, 67, 71, 72, 73, 75, and 77 were only produced in quantities
sufficient for a single crystal x-ray structure determination because these products were
produced only on a microscopic scale. The remaining ZIFs (ZIF-60, 61, 68, 69, 70, 74,
and 76), were prepared in quantities that allowed bulk characterizations (elemental
analysis, infrared spectroscopy and powder x-ray diffraction). In particular, ZIF-61, 68,
69, 70, and 76 were scaled up to gram quantities for a detailed investigation of their
porosity, thermal stability and chemical stability. The micro-synthesis conditions are
scalable to 10 gram scale by using the same reaction conditions in a larger volume (20
mL vial) and phase pure ZIF materials can thus be obtained. In this section, we report
detailed synthetic procedures for ZIF-2 to ZIF-77, which were discovered by the high
throughput method utilizing the 96-well micro-plates. It is noteworthy that the phase
purity of these mixed ligand ZIFs has always been under scrutiny since there is a
possibility of phase separation by those two individual ligands used for the mixed ligand
ZIF synthesis. To prove the phase purity of the bulk sample the PXRD and EA of the as-
synthesized and the activated samples are presented here. A comparison calculated/found
EA of the activated samples proved the phase purity of the sample. Activation conditions
of the respective samples and the corresponding TGA traces are described in a later
section of the manuscript. A detailed comparison of the PXRD patterns of the as-
synthesized and the activated samples with respect to their simulated PXRD patterns are
also presented. The ratio of these two ligands has been obtained from their respective
single crystal data.
4
(ZIF-2 crb): Zn(IM)2. 0.18 mL imidazole stock solution (0.15 M (1 M = 1 mol dm-3),
2.7 × 10-5 mol) and 0.12 mL Zn(NO3)2·4H2O stock solution (0.15 M, 1.8 × 10-5 mol)
were mixed together. After the glass plate was loaded with mixtures of stock solutions
dispensed by a programmed liquid handler (Gilson, model 215), it was covered with a
PTFE sheet, sealed by fastening the sheet with a metal clamp, then heated in an oven at
85 °C and allowed to react solvothermally for 72 h. The product was in the form of
prism-shaped single crystals. The unit cell dimensions of the ZIF thus obtained match
with the unit cell dimensions of ZIF-2 previously reported.
(ZIF-4 cag): Zn(IM)2. 0.18 mL imidazole stock solution (0.15 M, 2.7 × 10-5 mol) and
0.60 mL Zn(NO3)2·4H2O stock solution (0.15 M, 0.90 × 10-5 mol) were mixed together.
After the glass plate was loaded with mixtures of stock solutions dispensed by a
programmed liquid handler (Gilson, model 215), it was covered with a PTFE sheet,
sealed by fastening the sheet with a metal clamp, then heated in an oven at 100 °C and
allowed to react solvothermally for 72 h. The product was in the form of prism-shaped
single crystals. The unit cell dimensions of the ZIF thus obtained matches with the unit
cell dimensions of ZIF-4 previously reported.
(ZIF-8 sod): Zn(mIM)2. To a 0.225 mL 2-methylimidazole stock solution (0.20 M, 4.5 ×
10-5 mol), 0.075 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.5 × 10-5 mol) were added.
5
allowed to react solvothermally for 72 h. The product was in the form of cube-shaped
(ZIF-10 mer): Zn(IM)2. To a 0.20 mL imidazole stock solution (0.20 M, 4.0 × 10-5 mol)
in DMF 0.075 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.5 × 10-5 mol) were added.
single crystals. The unit cell dimensions of the ZIF thus obtained match with the unit cell
dimensions of ZIF-10 previously reported.
(ZIF-11 rho): Zn(bIM)2. To a 0.20 mL benzimidazole stock solution (0.20 M, 4.0 × 10-5
mol) in DEF 0.075 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.50 × 10-5 mol) in DEF
was added. After the glass plate was loaded with mixtures of stock solutions dispensed by
a programmed liquid handler (Gilson, model 215), it was covered with a PTFE sheet,
6
(ZIF-12 rho): Co(bIM)2. To a 0.20 mL benzimidazole stock solution (0.20 M, 4.0 × 10-5
mol) in DEF 0.075 mL Co(NO3)2·6H2O stock solution (0.20 M, 1.5 × 10-5 mol) in DEF
were added. After the glass plate was loaded with mixtures of stock solutions dispensed
by a programmed liquid handler (Gilson, model 215), it was covered with a PTFE sheet,
(ZIF-14 ana): Zn(eIM)2. To a 0.20 mL 2-ethylimidazole stock solution (0.20 M, 4.0 ×
10-5 mol) in DMF 0.075 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.50 × 10-5 mol) in
DMF was added. After the glass plate was loaded with mixtures of stock solutions
prism-shaped single crystals. The unit cell dimensions of the ZIF thus obtained match
with the unit cell dimensions of ANA structure (ZIF-14) previously reported.
(ZIF-20 lta): Zn(Pur)2. To a 0.18 mL purine stock solution (0.20 M, 3.6 × 10-5 mol) in
DMF 0.075 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.5 × 10-5 mol) in DMF were
added. After the glass plate was loaded with mixtures of stock solutions dispensed by a
7
(ZIF-21 lta): Co(Pur)2. To a 0.19 mL purin stock solution (0.20 M, 3.8 × 10-5 mol) in
DMF 0.075 mL Co(NO3)2·6H2O stock solution (0.20 M, 1.5 × 10-5 mol) in DMF was
single crystals. The unit cell dimension of the ZIF thus obtained matches with the unit
cell dimension of ZIF-21 previously reported previously reported.
8
(ZIF-60 mer): Zn(IM)1.5(mIM)0.5. 0.18 mL imidazole stock solution (0.15 M, 2.7 × 10-5
mol) and 0.060 mL 2-methylimidazole stock solution (0.15 M, 0.90 × 10-5 mol) was
mixed together. To this solution was added 0.060 mL Zn(NO3)2·4H2O stock solution
(0.15 M, 0.90 × 10-5 mol). After the glass plate was loaded with mixtures of stock
with a PTFE sheet, sealed by fastening the sheet with a metal clamp, then heated in an
oven at 85 °C and allowed to react solvothermally for 72 h. The product was in the form
of prism-shaped single crystals.
Elemental analysis C13H9N8Zn2 = Zn(IM)1.5(MeIM)0.5·(Me2NH)(H2O)3: Calcd. C, 33.17;
H, 6.55; N, 22.76. Found C, 33.28; H, 6.19; N, 22.13.
Elemental analysis (activated) C13H9N8Zn2 = Zn(IM)1.5(MeIM)0.5: Calcd. C, 37.44; H,
3.38; N, 26.87; Zn, 31.36. Found C, 36.97; H, 3.19; N, 27.13; Zn, 32.06.
FT-IR : (KBr 4000–400 cm-1): 3445(br), 3134(w), 2599(w), 2528(w), 2503(w), 1683(s),
1602(m), 1505(w), 1250(w), 1163(w), 955(w), 756(w), 675(w).
9
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Simulated
0
2 12 22 32
2θ (degree)
Figure S1. Comparison of the experimental PXRD pattern of as-prepared ZIF-60 (top)
with the one simulated from its single crystal structure (bottom). The very high degree of
correspondence between the patterns indicates that the bulk material has the same
structure as the single crystal.
(ZIF-61 zni): Zn(IM)(mIM). 0.12 mL imidazole stock solution (0.15 M, 1.8 × 10-5 mol)
and 0.12 mL 2-methylimidazole stock solution (0.15 M, 1.8 × 10-5 mol) was mixed
together. To this solution was added 0.060 mL Zn(NO3)2·4H2O stock solution (0.15 M,
0.90 × 10-5 mol). After the glass plate was loaded with mixtures of stock solutions
10
100 °C and allowed to react solvothermally for 96 h. The product was in the form of rod-
shaped single crystals.
Elemental analysis C7H9N4Zn = Zn(IM)(MeIM): Calcd. C, 38.99; H, 3.74; N, 25.99; Zn,
30.34. Found C, 39.17; H, 3.39; N, 26.13; Zn, 29.98.
1499(m), 1474(w), 1316(w), 1174(w), 1008(w), 837(w), 675(w), 420(s).
70000
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Experimental
10000
Simulated
0
2 12 22 32
2θ (degree)
11
(ZIF-62 cag): Zn(IM)1.75(bIM)0.25. 0.15 mL imidazole stock solution (0.20 M, 3.0 × 10-5
mol) and 0.075 mL benzimidazole stock solution (0.20 M, 1.5 × 10-5 mol) was mixed
prism-shaped single crystals.
(ZIF-64 dft): Zn(IM)2. To a 0.27 mL imidazole stock solution (0.20 M, 5.4 × 10-5 mol)
0.030 mL Zn(NO3)2·4H2O stock solution (0.20 M, 0.060 × 10-5 mol) was added. After the
glass plate was loaded with mixtures of stock solutions dispensed by a programmed
liquid handler (Gilson, model 215), it was covered with a PTFE sheet, sealed by fastening
the sheet with a metal clamp, then heated in an oven at 100 °C and allowed to react
solvothermally for 72 h. The product was in the form of rod-shaped single crystals.
(ZIF-65 sod): Co(nIM)2. To a 0.25 mL 2-nitroimidazole stock solution (0.20 M, 5.0 ×
10-5 mol), 0.050 mL Co(NO3)2·6H2O stock solution (0.20 M, 1.0 × 10-5 mol) was added.
single crystals.
12
(ZIF-67 sod): Co(mIM)2. To a 0.225 mL 2-nitroimidazole stock solution (0.20 M, 4.5 ×
10-5 mol), 0.075 mL Co(NO3)2·6H2O stock solution (0.20 M, 1.5 × 10-5 mol) was added.
single crystals.
(ZIF-68 gme): Zn(nIM)(bIM). 0.180 mL 2-nitroimidazole stock solution (0.20 M, 3.6 ×
10-5 mol) and 0.060 mL benzimidazole stock solution (0.20 M, 1.2 × 10-5 mol) was mixed
yellow colored prism-shaped single crystals.
Elemental analysis C10H9N5O2Zn = Zn(NO2IM)(PhIM)·(DMF)(H2O)2: Calcd. C, 36.10;
H, 3.33; N, 21.05. Found C, 35.47; H, 2.89; N, 21.83.
Elemental analysis (activated) C10H9N5O2Zn = Zn(NO2IM)(PhIM): Calcd. C, 40.49; H,
2.38; N, 23.62; O, 10.79; Zn, 22.05. Found C, 40.09; H, 2.12; N, 23.60; O, 11.44; Zn,
21.95.
13
2523(m), 2319(w), 1678(w), 1479(w), 1367(w), 1245(w), 1174(w), 909(s), 741(w),
669(w), 552(m).
35000
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Simulated
0
2 12 22 32
2 θ (degree)
(ZIF-69 gme): Zn(nIM)(5cbIM). 0.12 mL 2-nitroimidazole stock solution (0.20 M, 2.4
× 10-5 mol) and 0.12 mL 5-chlorobenzimidazole stock solution (0.20 M, 2.4 × 10-5 mol)
was mixed together. To this solution was added 0.060 mL Zn(NO3)2·4H2O stock solution
14
oven at 100 °C and allowed to react solvothermally for 72 h. The product was in the form
of yellow colored prism-shaped single crystals.
Elemental analysis C10H8N4O2ClZn = Zn(NO2IM)(5ClPhIM)·(H2O)4: Calcd. C, 32.78;
H, 4.44; N, 17.65. Found C, 31.89; H, 4.39; N, 17.13.
Elemental analysis (activated) C10H8N4O2ClZn = Zn(NO2IM)(5ClPhIM): Calcd. C,
36.28; H, 1.83; N, 21.16; O, 9.67; Cl, 10.74; Zn, 19.75. Found C, 35.90; H, 1.81; N,
20.76; O, 9.82; Zn, 19.51.
2660(m), 2523(w), 2319(w), 1667(w), 1470(w), 1364(w), 1291(w), 1240(s), 1174(w),
807(w), 659(m), 603(w).
15
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Simulated
0
2 12 22 32
2θ(degree)
16
(ZIF-70 gme): Zn(IM)1.13(nIM)0.87. 0.12 mL 2-nitroimidazole stock solution (0.20 M,
2.4 × 10-5 mol) and 0.12 mL imidazole stock solution (0.20 M, 2.4 × 10-5 mol) was mixed
prism-shaped single crystals.
Elemental analysis C6H5.13N4.87O1.74Zn = Zn(IM)1.10(NO2IM)0.90(DMF)(H2O)4: Calcd. C,
35.30; H, 4.44; N, 20.59. Found C, 35.17; H, 4.39; N, 20.13.
Elemental analysis (activated) C6H5.13N4.87O1.74Zn = Zn(IM)1.10(NO2IM)0.90: Calcd. C,
29.93; H, 2.14; N, 28.34; O, 11.57; Zn, 27.16. Found C, 29.77; H, 2.12; N, 28.36; O,
11.90; Zn, 27.01.
2518(m), 2329(w), 1678(w), 1510(w), 1372(w), 1168(w), 1102(w), 669(s).
17
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Simulated
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2θ (degree)
18
(ZIF-71 rho): Zn(dcIM)2. To a 0.24 mL 4,5-dichloroimidazole stock solution (0.075 M,
1.8 × 10-5 mol) 0.060 mL Zn(NO3)2·4H2O stock solution (0.075 M, 0.45 × 10-5 mol) was
allowed to react solvothermally for 96 h. The product was in the form of block-shaped
single crystals.
(ZIF-72 lcs): Zn(dcIM)2. To a 0.24 mL 4,5-dichloroimidazole stock solution (0.20 M,
4.8 × 10-5 mol) 0.060 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.2 × 10-5 mol) in DEF
was added. After the glass plate was loaded with mixtures of stock solutions dispensed by
a programmed liquid handler (Gilson, model 215), it was covered with a PTFE sheet,
allowed to react solvothermally for almost 6 days. The product was in the form of prism-
shaped single crystals.
(ZIF-73 frl): Zn(nIM)1.74(dmbIM)0.26. 0.12 mL 2-nitroimidazole stock solution (0.20 M,
2.4 × 10-5 mol) and 0.12 mL 5,6-dimethylbenzimidazole stock solution (0.20 M, 0.90 ×
10-5 mol) was mixed together. To this solution was added 0.060 mL Zn(NO3)2·4H2O
stock solution (0.15 M, 0.90 × 10-5 mol). After the glass plate was loaded with mixtures
of stock solutions dispensed by a programmed liquid handler (Gilson, model 215), it was
covered with a PTFE sheet, sealed by fastening the sheet with a metal clamp, then heated
19
in an oven at 85 °C and allowed to react solvothermally for 72 h. The product was in the
form of prism-shaped single crystals.
(ZIF-74 gis): Zn(nIM)(dmbIM). 0.18 mL 2-nitroimidazole stock solution (0.20 M, 3.6
× 10-5 mol) and 0.060 mL 5,6-dimethylbenzimidazole stock solution (0.20 M, 1.2 × 10-5
mol) was mixed together. To this solution was added 0.060 mL Zn(NO3)2·4H2O stock
solution (0.15 M, 0.90 × 10-5 mol). After the glass plate was loaded with mixtures of
stock solutions dispensed by a programmed liquid handler (Gilson, model 215), it was
covered with a PTFE sheet, sealed by fastening the sheet with a metal clamp, then heated
in an oven at 85 °C and allowed to react solvothermally for 5 days. The product was in
the form of rod-shaped single crystals.
Elemental analysis C12H13N5O2Zn = Zn(NO2IM)(5,6Me2PhIM): Calcd. C, 39.28; H,
5.36; N, 28.65. Found C, 39.47; H, 4.39; N, 27.13.
1469(m), 1342(w), 1286(w), 1092(w), 939(w), 802(w), 669(w), 603(s).
20
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1000 Simulated
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2 12 2θ (degree) 22 32
21
(ZIF-75 gis): Co(nIM)(dmbIM). 0.12 mL imidazole stock solution (0.15 M, 1.8 × 10-5
mol) and 0.12 mL 5,6-dimethylbenzimidazole stock solution (0.15 M, 0.90 × 10-5 mol)
was mixed together. To this solution was added 0.060 mL Co(NO3)2·6H2O stock solution
oven at 85 °C and allowed to react solvothermally for 5 days. The product was in the
form of pink colored rod -shaped single crystals.
(ZIF-76 lta): Zn(IM)(cbIM). 0.15 mL imidazole stock solution (0.15 M, 2.25 × 10-5
mol) and 0.075 mL 5-chlorobenzimidazole stock solution (0.15 M, 1.13 × 10-5 mol) was
mixed together. To this solution was added 0.075 mL Zn(NO3)2·4H2O stock solution
oven at 65 °C and allowed to react solvothermally for 5 days. The product was in the
form of hexagon-shaped single crystals.
Elemental analysis C8H13N5Zn = Zn(IM)1.5(5ClPhIM)0.5·(H2O)4: Calcd. C, 33.96; H,
5.57; N, 18.05. Found C, 33.27; H, 5.39; N, 18.13.
Elemental analysis (activated) C8H13N5Zn = Zn(IM)1.5(5ClPhIM)0.5: Calcd. C, 39.28; H,
5.36; N, 28.65. Found C, 39.47; H, 4.39; N, 27.13.
1469(m), 1342(w), 1286(w), 1092(w), 939(w), 802(w), 669(w), 603(s).
22
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0
2 7 12 17 22 27 32
2θ (degree)
(ZIF-77 frl): Zn(nIM)2. To a 0.26 mL 2-nitroimidazole stock solution (0.20 M, 5.2 × 10-
5
mol) 0.060 mL Zn(NO3)2·4H2O stock solution (0.20 M, 1.2 × 10-5 mol) was added.
23
single crystals.
24
Section S2. Representative optical photographs of ZIFs crystals (0.1 to 1 mm) and
single crystal x-ray diffraction data collection, structure solution and refinement
procedures.
General Data Collection and Refinement Procedures:
Data were collected on a Bruker SMART APEXII three circle diffractometer equipped
with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu
Kα radiation (λ = 1.5418 Å). The incident x-ray beam was focused and monochromated
using Bruker Excalibur Gobel mirror optics. Crystals of ZIF-60, 61, 62, and 70 were
mounted in flame sealed capillaries containing a small amount of mother liquor to
prevent desolvation during data collection. Photographic images of wells containing
crystals (0.1 to 1.0 mm) are shown in Fig. S8. All crystals of other ZIFs reported in the
paper were mounted on nylon CryoLoops (Hampton Research) with Paraton-N (Hampton
Research).
Initial scans of each specimen were performed to obtain preliminary unit cell parameters
and to assess the mosaicity (i.e. breadth of spots between frames) of the crystal to select
the required frame width for data collection. In every case frame widths of 0.5° were
judged to be appropriate and full hemispheres of data were collected using the Bruker
APEX21 software suite to carry out overlapping φ and ω scans at three different detector
(2θ) settings (2θ = 28, 60, 100°). Following data collection, reflections were sampled
from all regions of the Ewald sphere to redetermine unit cell parameters for data
integration and to check for rotational twinning using CELL_NOW2. In no data collection
was evidence for crystal decay encountered. Following exhaustive review of collected
frames the resolution of the dataset was judged. Data were integrated using Bruker
25
APEX2 V 2.13 software with a narrow frame algorithm and a 0.400 fractional lower limit
of average intensity. Data were subsequently corrected for absorption by the program
SADABS4. The absorption coefficient (μ) ranges between 1-6 for most of the ZIFs
reported in this paper. However it is note worthy that μ is based on the atomic contents
and this is uncertain for most of the structures diffuse electron density of the guest
molecule, this number is imprecise. Space group determination and tests for merohedral
twinning were carried out using XPREP3. ZIF-68, 69, and 70 were found to be
merohedrally twinned. This could possibly be the reason for their higher R–factor
although all the atomic positions were defined. In all other cases the highest possible
space group was chosen and no indication of merohedral twinning was observed.
All structures were solved by direct methods and refined using the SHELXTL 975
software suite. Atoms were located from iterative examination of difference F-maps
following least squares refinements of the earlier models. Final models were refined
anisotropically (if the number of data permitted) until full convergence was achieved.
However, several structures contained disordered components within the frameworks. In
these cases occupancies X and (1 – X) and equivalent displacement parameters were
assigned to each pair of atoms in the disordered groups and X was refined as an
independent free variables. Hydrogen atoms were placed in calculated positions (C—H =
0.93 Å) and included as riding atoms with isotropic displacement parameters 1.2–1.5
times Ueq of the attached C atoms. Modeling of electron density within the voids of the
frameworks did not lead to identification of guest entities in all structures due to the
disordered contents of the large pores in the frameworks. This challenge, which is typical
of highly porous crystals that contain solvent filled pores, lies in the raw data where
26
observed strong (high intensity) scattering becomes limited to ~1.0 Å at best, with higher
resolution data present but weak (low intensity). As is a common strategy for improving
x-ray data, increasing the exposure time of the crystal to x-rays did not improve the
quality of the high angle data in these cases, as the intensity from low angle data
saturated the detector and minimal improvement in the high angle data was achieved.
Additionally, diffuse scattering from the highly disordered solvent in the void spaces
within the crystal and from the capillary used to mount the crystal contributes to the
background noise and the 'washing out' of high angle data. The only optimal crystals
suitable for analysis were generally small and weakly diffracting, and unfortunately,
larger crystals, which would usually improve the quality of the data, presented a lowered
degree of crystallinity and attempts to optimize the crystal growing conditions for large
high-quality specimens has not yet been fruitful. For ZIF-60, 61, 62, and 70 data have
been collected at elevated temperatures (-15 °C, rather than -120 to -100 °C). For other
ZIFs reported in this paper it was found that data collection at -120 °C was optimal for
obtaining the best data. In such cases the modeling of the disordered guest entities
becomes intractable because they become frozen into highly disordered arrays. Thus,
electron density within void spaces, which could not be assigned to any definite guest
entity, was modeled as isolated oxygen atoms, and the foremost errors in all the models
lies with assignment of guest electron density. To prove the correctness of the atomic
positions in the framework the application of the SQUEEZE6 routine of A. Spek had been
performed. However atomic co-ordinates for the “non-SQUEEZE” structures have also
been presented and the CIFs were also submitted for the cases where the program
SQUEEZE has been employed. The assignment and refinement of the metal-organic ZIF
27
framework atoms was unambiguous, as judged by the resulting bond and angle metrics
which are chemically accurate and precise values. All structures were examined using the
Adsym subroutine of PLATON7 to assure that no additional symmetry could be applied to
the models. All ellipsoids in ORTEP diagrams are displayed at the 30% probability level
unless noted otherwise. For all structures we note that the elevated R-values are
commonly encountered in MOF crystallography, for the reasons expressed above, by us
and other research groups 8-17
1. Bruker (2005). APEX2. Version 5.053. Bruker AXS Inc., Madison,Wisconsin,
USA.
2. Sheldrick, G. M. (2004). CELL_NOW. University of Göttingen, Germany.
Steiner, Th. (1998). Acta Cryst. B54, 456–463.
3. Bruker (2004). SAINT-Plus (Version 7.03). Bruker AXS Inc., Madison,
Wisconsin, USA.
4. Sheldrick, G. M. (2002). SADABS (Version 2.03) and TWINABS (Version
1.02).University of Göttingen, Germany.
5. Sheldrick, G. M. (1997). SHELXS ‘97 and SHELXL ‘97. University of Göttingen,
Germany.
6. WINGX
7. Spek, A. L. (2005) PLATON, A Multipurpose Crystallographic Tool, Utrecht
University, Utrecht, The Netherlands.
8. Dakin, L. A., Ong P. C., Panek, J. S., Staples, R. J. & Stavropoulos, P.
Organometallics 19, 2896–2908 (2000).
28
9. Noro, S., Kitaura, R., Kondo, M., Kitagawa, S., Ishii, T., Matsuzaka, H. &
Yamashita, M. J. Am. Chem. Soc. 124, 2568–2583 (2002).
10. Eddaoudi, M., Kim, J., Vodak, D., Sudik, A., Wachter, J., O’Keeffe, M. & Yaghi,
O. M. Proc. Natl. Acad. Sci. U.S.A. 99, 4900–4904 (2002).
11. Heintz, R. A., Zhao, H., Ouyang, X., Grandinetti, G., Cowen, J. & Dunbar, K. R.
Inorg. Chem. 38, 144–156 (1999).
12. Biradha, K., Hongo, Y. & Fujita, M. Angew. Chem. Int. Ed. 39, 3843–3845
(2000).
13. Grosshans, P., Jouaiti, A., Hosseini, M. W. & Kyritsakas, N. New J. Chem, (Nouv.
J. Chim.) 27, 793–797 (2003).
14. Takeda, N., Umemoto, K., Yamaguchi, K. & Fujita, M. Nature (London) 398,
794–796 (1999).
15. Eddaoudi, M., Kim, J., Rosi, N., Vodak, D., Wachter, J., O’Keeffe, M. & Yaghi,
O. M. Science 295, 469–472 (2002).
16. Kesanli, B., Cui, Y., Smith, M. R., Bittner, E. W., Bockrath, B. C. & Lin, W.
Angew. Chem. Int. Ed. 44, 72–75 (2005).
17. Cotton, F. A., Lin, C. & Murillo, C. A. Inorg. Chem. 40, 478–484 (2001).
29
Fig. S8. Representative optical photographs of zeolitic imidazolate frameworks (ZIFs)
crystals (0.1 to 1 mm) found in the wells after reacting reagents using the high-
throughput method.
30
ZIF-60 (MER─ Tetragonal)
Experimental and Refinement Details for ZIF-60
A colorless prismatic crystal (0.25 × 0.20 × 0.18 mm3) of ZIF-60 was placed in a 0.4 mm
diameter borosilicate capillary along with a small amount of mother liquor. The capillary
was flame sealed and mounted on a SMART APEXII three circle diffractometer
equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to
generate Cu Kα radiation (λ = 1.5418 Å) while being flash frozen to 258(2) K in a liquid
N2 cooled stream of nitrogen. A total of 36256 reflections were collected of which 2911
were unique and 2404 of these were greater than 2σ(I). The range of θ was from 2.29 to
59.36°. Analysis of the data showed negligible decay during collection. The structure was
solved in the tetragonal I4/mmm space group, with Z = 4, using direct methods. Atoms
C2 and C4 were found to be disordered and were refined isotropically with the occupancy
for each group modeled as its own independent free variable (X, 1 – X). All other non-
hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres
riding the coordinates of their parent atoms. Modeling of electron density within the
voids of the frameworks did not lead to identification of guest entities in all structures
due to the lowered resolution of the data. The attempts made to model the guests (solvent
molecules) did not lead to identification of guest entities in all structures due to the
limited periodicity of the solvent molecules in the crystals. Since the solvent is not
bonded to the framework this can be expected for the MOF structures. Many atomic co-
ordinates that have been attributed to solvent molecules lie on a special position.
However, very high displacement parameters, high esd’s and partial occupancy due to the
disorder make it impossible to determine accurate positions for these solvent molecules.
31
Thus, electron density within void spaces which could not be assigned to any definite
guest entity was modeled as isolated carbon and oxygen atoms, and the foremost errors in
all the models lies with assignment of guest electron density. To prove the correctness of
the atomic positions in the framework the application of the SQUEEZE routine of A.
Spek has been performed. However atomic co-ordinates for the “non-SQUEEZE”
structures are also presented. The unit cell of ZIF-60 contains 1.5 imidazole and 0.5 2-
methyl imidazole (3:1) per zinc. Final full matrix least-squares refinement on F2
converged to R1 = 0.0360 (F >2σF)) and wR2 = 0.1157 (all data) with GOF = 1.093. For
the structure where the SQUEEZE program has not been employed, final full matrix
least-squares refinement on F2 converged to R1 = 0.0674 (F >2σF)) and wR2 = 0.2605 (all
data) with GOF = 1.059. When only framework atoms are included in the latter structure
factor calculation, the residual electron density in the F-map is located within the pores of
ZIF-60.
32
Table S1. Crystal data and structure refinement for ZIF-60.
Empirical formula C87 H56 N36 O4 Zn8

Formula weight 2192.80
Temperature 258(2) K
Wavelength 1.54178 Å
Crystal system Tetragonal
Space group I4/mmm
Unit cell dimensions a = 27.2448(3) Å α = 90°
b = 27.2448(3) Å β = 90°
c = 19.2254(3) Å γ = 90°
Volume 14270.6(3)
Z 4
Density (calculated) 1.021
Absorption coefficient 1.839
F(000) 4408
Crystal size 0.25 × 0.20 × 0.18 mm3
Theta range for data collection 2.29- 59.36
Index ranges -30 <= h <= 24, -30 <= k <= 28, -21 <= l <= 19
Reflections collected 36256
Independent reflections 2911 [Rint= 0.0247]
Completeness to theta = 59.36° 99.7%
Absorption correction Semi-empirical from equivalents
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 2911/0/146
Goodness-of-fit on F2 1.059
Final R indices [I>2sigma(I)] R1 = 0.0674, wR2 = 0.2421
R indices (all data) R1 = 0.0761, wR2 = 0.2605
Largest diff. peak and hole 0.634 and -0.444 e.Å-3
33
Table S2. Crystal data and structure refinement for ZIF-60 (SQUEEZE).
Empirical formula C13 H14 N8 Zn2

Space group I4/mmm
b = 27.2448(3) Å β = 90°
c = 19.2254(3) Å γ = 90°
Volume 14270.6(3)
Z 16
F(000) 3328.0
Crystal size 0.25 × 0.20 × 0.18 mm3
Index ranges -30 <= h <= 24, -30 <= k <= 28, -21 <= l <= 19
34
Figure S9. ORTEP drawing of an asymmetric unit of ZIF-60, excluding the guest
entities.
35
ZIF-61 (ZNI─ Tetragonal)
diameter borosilicate capillary along with a small amount of mother liquor. The capillary
was flame sealed and mounted on a SMART APEXII three circle diffractometer
generate Cu Kα radiation (λ = 1.5418 Å) radiation while being flash frozen to 258(2) K in
a liquid N2 cooled stream of nitrogen. A total of 17067 reflections were collected of
which 1443 were unique and 1335 of these were greater than 2σ(I). The range of θ was
from 3.76 to 64.55°. Analysis of the data showed negligible decay during collection. The
structure was solved in the tetragonal I41/acd space group with Z = 2 using direct
methods. Atoms C1, C5, and C6 were found to be disordered and were refined
anisotropically with the occupancy for each group modeled as its own independent free
variable (X, 1 – X). All other non-hydrogen atoms were also refined anisotropically with
hydrogen atoms generated as spheres riding the coordinates of their parent atoms.
Modeling of electron density within the voids of the frameworks did not lead to
identification of guest entities in all structures due to the lowered resolution of the data.
The unit cell of ZIF-61 contains one imidazole and one 2-methylimidazole (1:1) per zinc.
Final full matrix least-squares refinement on F2 converged to R1 = 0.0523 (F >2σF)) and
wR2 = 0.1339 (all data) with GOF = 1.148.
36
Empirical formula C13 H14 N8 Zn2

Space group I41/acd
b = 23.4803(3) Å β = 90°
c = 12.5545(3) Å γ = 90°
Volume 6921.6(3)
Z 2
F(000) 3312.0
Crystal size 0.21 × 0.18 × 0.16 mm3
Index ranges -25 <= h <= 27, -26 <= k <= 27, -12 <= l <= 14
37
Figure S10. ORTEP drawing of the asymmetric unit of ZIF-61, excluding the guest
entities.
38
ZIF-62 (CAG─ Orthorhombic)
diameter borosilicate capillary with a small amount of mother liquor. The capillary was
flame sealed and mounted on a SMART APEXII three circle diffractometer equipped
with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu
Kα radiation (λ = 1.5418 Å) radiation while being flash frozen to 258(2) K in a liquid N2
cooled stream of nitrogen. A total of 17208 reflections were collected, of which 2873
solved in the orthorhombic Pbca space group with Z = 2 using direct methods. Modeling
of electron density within the void of the frameworks leads to identification of one DMF
guest molecule in the asymmetric unit. These imidazole linkers have no crystallographic
symmetry. The contents per 2 Zn (independent) = 4 linkers; 3 are unsubstituted imidazole
with no disorder and the fourth is 0.375(11) benzimidazole and 0.625(11) imidazole.
Note that this fourth position can contain a maximum of 50% benzimidazole because a
center of symmetry in this space group would bring the benzene rings related by this
center into contact with each other. No such limitation exists for the unsubstituted
imidazole. With the exception of the 4 partial occupancy benzene carbon atoms and the
solvent atoms, all non-hydrogen atoms have been refined anisotropically. All hydrogen
atoms have been placed in geometrically located positions and their displacement
parameters are tied to those of the attached carbon atoms. The unit cell of ZIF-62
contains 1.812 imidazole and 0.187 benzimidazole per zinc. Final full matrix least-
39
squares refinement on F2 converged to R1 = 0.0590 (F >2σF)) and wR2 = 0.1890 (all data)
with GOF = 1.139.
40

Crystal system Orthorhombic
Space group Pbca
b = 15.6620(14) Å β = 90°
c = 18.2073(19) Å γ = 90°
Volume 4466.2(7)
Z 2
F(000) 1810
Crystal size 0.20 × 0.15 × 0.12 mm3
Index ranges -16 <= h <= 16, -14 <= k <= 16, -19 <= l <= 19
Data / restraints / parameters 2873/11/ 236
41
Figure S11. ORTEP drawing of two zinc atoms surrounded by seven linkers of ZIF-62
excluding the guest entities. Imidazole in the center is shared by two crystallographically
different zinc atoms. This central imidazole is the major (60%) occupant.
Figure S12. ORTEP drawing of two zinc atoms surrounded by seven linkers of ZIF-62
excluding the guest entities. Benzimidazole in the center is shared by two
crystallographically different zinc atoms. This central benzimidazole is the minor (40%)
occupant.
42
ZIF-64 (CRB─Monoclinic)
A colorless needle shaped crystal (0.25 × 0.14 × 0.12 mm3) of ZIF-64 was placed in a 0.7
mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton
Research). The loop was mounted on a SMART APEXII three circle diffractometer
N2 cooled stream of nitrogen. A total of 17208 reflections were collected, of which 2873
solved in the monoclinic P2/n space group with Z = 16 using direct methods. Atoms C6
and C21 were found to be disordered and were refined anisotropically with the
occupancy for each group modeled as its own independent free variable (X, 1 – X). All
other non-hydrogen atoms were refined anisotropically with hydrogen atoms generated as
spheres riding the coordinates of their parent atoms. Although the unit cell has a = c and
all angles 90˚, Rint is 0.4189 for a tetragonal cell and 0.1546 for a monoclinic cell.
XPREP prefers a monoclinic cell. The 4 independent Zn atoms of the monoclinic space
group drop to 2 in the space group P4/n, but in the later space group the model refines
poorly (R ∼ 28%) and the disordered carbon atoms of the imidazole retain their disorder.
An inspection of hkl with b as the unique axis has h 0 0 not equal to 0 0 l. Also, although
there are no strong 0 k 0 reflections, the odd k are not entirely absent. The n-glide absence
(h 0 l, h 1 l ≠ 2n) are required for both space groups to be tested. Modeling of electron
density within the void of the frameworks leads to identification of 2.5 DMF guest
43
molecules in the asymmetric unit. These imidazole linkers have no crystallographic
symmetry. The unit cell of ZIF-64 contains two imidazole linkers per zinc. All hydrogen
atoms have been placed in geometrically located positions and their displacement
parameters are tied to those of the attached carbon atoms. Final full matrix least-squares
refinement on F2 converged to R1 = 0.1116 (F >2σF)) and wR2 = 0.2573 (all data) with
GOF = 1.083.
44
Empirical formula C7.75 H9.25 N4.56 O0.56 Zn

Crystal system Monoclinic
Space group P2/n
b = 9.906(2) Å β = 90.00(2)°
c = 21.110(4) Å γ = 90°
Volume 4414.6(14)
Z 16
F(000) 1955
Crystal size 0.25 × 0.14 × 0.12 mm3
Index ranges -21 <= h <= 21, -10 <= k <= 9, -21 <= l <= 17
Data / restraints / parameters 2873/0/ 497
45
Figure S13. ORTEP drawing of four unique zinc atoms and eight unique imdazole
linkers of ZIF-64 excluding the guest entities.
46
ZIF-65 (SOD─ CUBIC)
diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research).
The loop was mounted on a SMART APEXII three circle diffractometer equipped with a
CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Kα
radiation (λ = 1.5418 Å) while being flash frozen to 153(2) K in a liquid N2 cooled
stream of nitrogen. A total of 7062 reflections were collected of which 264 were unique
and 257 of these were greater than 2σ(I). The range of θ was from 3.62 to 36.79°.
Analysis of the data showed negligible decay during collection. The structure was solved
in the cubic I-43m space group, with Z = 2, using direct methods. All non-hydrogen
atoms were refined anisotropically with hydrogen atoms generated as spheres riding the
coordinates of their parent atoms. Modeling of electron density within the voids of the
frameworks did not lead to identification of guest entities in all structures due to the
lowered resolution of the data. Since the solvent is neither bonded to the framework nor
tightly packed into the voids, this can be expected for the MOF structures. The unit cell
of ZIF-65 contains two 2-nitroimidazole linker per cobalt. Final full matrix least-squares
GOF = 1.113. When only framework atoms are included in the structure factor
calculation, the residual electron density in the F-map is located within the pores of ZIF-
65.
47
Empirical formula C36 H24 Co6 N36 O24

Crystal system Cubic
Space group I-43m
b = 17.2715(4) Å β = 90°
c = 17.2715(4) Å γ = 90°
Volume 5152.2(2)
Z 2
F(000) 1692
Crystal size 0.20 × 0.16 × 0.12 mm3
Theta range for data collection 3.62 to 36.79°
Index ranges -13 <= h <= 13, -13 <= k <= 13, -12 <= l <= 13
Completeness to theta = 36.79° 100%
2
Goodness-of-fit on F 1.113
48
entities.
49
ZIF-67 (SOD─ CUBIC)
in the cubic I-43m space group, with Z = 4, using direct methods. All non-hydrogen
frameworks did not lead to identification of guest entities in any of the structures due to
the lowered resolution of the data. The attempts made to model the guests (solvent
molecules) did not lead to identification of guest entities in any of the structures due to
the limited periodicity of the solvent molecules in the crystals. Since the solvent is neither
bonded to the framework nor tightly packed into the voids, this can be expected for the
MOF structures. Thus, electron density within void spaces which could not be assigned to
any definite guest entity was modeled as isolated oxygen atoms, and the foremost errors
in all the models lie with the assignment of guest electron density. To assess the
correctness of the atomic positions in the framework, the application of the SQUEEZE
50
routine of A. Spek has been performed. However, atomic co-ordinates for the “non-
SQUEEZE” structures are also presented. The unit cell of ZIF-67 contains two 2-
methylimidazole linkers per cobalt. Final full matrix least-squares refinement on F2
converged to R1 = 0.0295 (F >2σF)) and wR2 = 0.0825 (all data) with GOF = 1.118. For
the structure where the SQUEEZE program has not been employed, final full matrix
least-squares refinement on F2 converged to R1 = 0.0724 (F >2σF)) and wR2 = 0.2138 (all
data) with GOF = 1.193. When only framework atoms are included in the latter structure
factor calculation, the residual electron density in the F-map is located within the pores of
ZIF-67.
51

Space group I-43m
b = 16.9589(3) Å β = 90°
c = 16.9589(3) Å γ = 90°
Volume 4877.45(15)
Z 4
F(000) 1420
Crystal size 0.20 × 0.16 × 0.12 mm3
Index ranges -14 <= h <= 15, -15 <= k <= 14, -14 <= l <= 15
2
52
Empirical formula C8 H10 Co N4

Space group I-43m
b = 16.9589(3) Å β = 90°
c = 16.9589(3) Å γ = 90°
Volume 4877.45(15)
Z 4
F(000) 1420
Crystal size 0.20 × 0.16 × 0.12 mm3
Index ranges -14 <= h <= 15, -15 <= k <= 14, -14 <= l <= 15
2
53
entities.
54
ZIF-68 (GME─ HEXAGONAL)
stream of nitrogen. A total of 30723 reflections were collected of which 1382 were
unique and 1209 of these were greater than 2σ(I). The range of θ was from 1.91 to
40.66°. Analysis of the data showed negligible decay during collection. Space groups
P63/mmc (hexagonal) and P-31c (trigonal) were suggested by XPREP with very similar
CFOM (7.60 vs 7.32). The structure was solved in the hexagonal P63/mmc space group,
with Z = 24, using direct methods. Atoms Zn1, N2, N3, C1, and C11 were refined
anisotropically. All other non-hydrogen atoms were refined isotropically with hydrogen
atoms generated as spheres riding the coordinates of their parent atoms. ZIF-68 is
composed of one 2-nitroimidazole and one benzimidazole per Zn. An asymmetric unit
contains one half nitroimidazole (linker with mirror symmetry, no disorder), one half
benzimidazole (linker with mirror symmetry, no disorder), one half nitroimidazole (linker
with mirror symmetry), and one half benzimidazole (linker with a 2-fold axis). The
attempts made to model the guests (solvent molecules) did not lead to identification of
guest entities in any of the structures due to the limited periodicity of the solvent
55
molecules in the crystals. Since the solvent is neither bonded to the framework nor tightly
packed into the voids, solvent disorder can be expected for the MOF structures. Thus,
electron density within void spaces which could not be assigned to any definite guest
entity was modeled as isolated carbon atoms, and the foremost errors in all the models
lies with the assignment of guest electron density. To assess the correctness of the atomic
positions in the framework, the application of the SQUEEZE routine of A. Spek has been
performed. It should be noted that the precision of this model is low; however, the
structure is reported to display the framework for ZIF-68 as isolated in the crystalline
form. Other supporting characterization data (vide infra Materials and Methods) are
consistent with the crystal structure. Final full matrix least-squares refinement on F2
converged to R1 = 0.1367 (F >2σF)) and wR2 = 0.4772 (all data) with GOF = 2.374.
When only framework atoms are included in the latter structure factor calculation, the
residual electron density in the F-map is located within the pores of ZIF-68.
56
Empirical formula C7.06 H4.94 N3.53 O1.59 Zn0.71

Crystal system Hexagonal
Space group P63/mmc
b = 26.6407(4) Å β = 90°
c = 18.4882(4) Å γ = 120°
Volume 11363.6(3)
Z 24
F(000) 3600
Crystal size 0.24 × 0.18 × 0.16 mm3
Index ranges -22 <= h <= 22, -22 <= k <= 23, -14 <= l <= 16
2
57
Figure S16. ORTEP drawing of zinc atom surrounded by four linkers of ZIF-69
excluding the guest entities.
58
with Z = 24, using direct methods. Atoms N1, C12, O3 and N9 were found to be
disordered and were refined anisotropically with the occupancy for each group modeled
as its own independent free variable (X, 1 – X). All other non-hydrogen atoms were
refined anisotropically with hydrogen atoms generated as spheres riding the coordinates
of their parent atoms. ZIF-69 is composed of one 2-nitroimidazole and one
monochlorobenzoimidazole per Zn. An asymmetric unit contains one half nitroimidazole
(linker with mirror symmetry, no disorder), one half monochorobenzoimidazole (linker
with mirror symmetry, no disorder), one half nitroimidazole (linker with mirror
symmetry, disorder with separable atoms for NO2 and HCCH), and one half
59
monochlorobenzoimidazole (linker with a 2-fold axis, disorder with separable atoms for
N and for Cl). The attempts made to model the guests (solvent molecules) did not lead to
identification of guest entities in any of the structures due to the limited periodicity of the
solvent molecules in the crystals. Since the solvent is neither bonded to the framework
nor tightly packed into the voids, solvent disorder can be expected for the MOF
structures. Thus, electron density within void spaces which could not be assigned to any
definite guest entity was modeled as isolated carbon atoms, and the foremost errors in all
the models lies with the assignment of guest electron density. To assess the correctness of
the atomic positions in the framework, the application of the SQUEEZE routine of A.
Spek has been performed. However, atomic co-ordinates for the “non-SQUEEZE”
structures are also presented. It should be noted that the precision of this model is low;
however, the structure is reported to demonstrate the nature of the framework of ZIF-69.
Other supporting characterization data (vide infra Materials and Methods) agree with the
structure. Final full matrix least-squares refinement on F2 converged to R1 = 0.0716 (F
>2σF)) and wR2 = 0.1978 (all data) with GOF = 1.011. For the structure where the
SQUEEZE program has not been employed, final full matrix least-squares refinement on
F2 converged to R1 = 0.0930 (F >2σF)) and wR2 = 0.3169 (all data) with GOF = 1.671.
60
Empirical formula C12.58 H6 Cl N5.25 O2.50 Zn

Space group P63/mmc
b = 26.0840(18) Å β = 90°
c = 19.4082(18) Å γ = 120°
Volume 11435.7(15)
Z 24
F(000) 4446
Crystal size 0.24 × 0.18 × 0.16 mm3
Index ranges -23 <= h <= 22, -23 <= k <= 23, -16 <= l <= 17
61
Empirical formula C10.25 H6 Cl N5.25 O2.75 Zn

Space group P63/mmc
b = 26.0840(18) Å β = 90°
c = 19.4082(18) Å γ = 120°
Volume 11435.7(15)
Z 24
F(000) 4158
Crystal size 0.24 × 0.18 × 0.16 mm3
Index ranges -23 <= h <= 22, -23 <= k <= 23, -16 <= l <= 17
62
excluding the guest entities.
63
diameter borosilicate capillary along with a small amount of mother liquor. The sealed
capillary was mounted on a SMART APEXII three circle diffractometer equipped with a
with Z = 4, using direct methods. Atoms C6 and C7 were found to be disordered and
were refined anisotropically with the occupancy for each group modeled as its own
independent free variable (X, 1 – X). All other non-hydrogen atoms were refined
anisotropically with hydrogen atoms generated as spheres riding the coordinates of their
parent atoms. The attempts made to model the guests (solvent molecules) did not lead to
identification of guest entities in any of the structures due to the limited periodicity of the
solvent molecules in the crystals. Since the solvent is neither bonded to the framework
nor tightly packed into the voids, solvent disorder can be expected for the MOF
structures. Thus, electron density within void spaces which could not be assigned to any
definite guest entity was modeled as isolated carbon atoms, and the foremost errors in all
the models lie with the assignment of guest electron density. “Solvent” is 4 atoms refined
64
as carbon atoms of undefined solvent, located in a void of the framework. To assess the
correctness of the atomic positions in the framework, the application of the SQUEEZE
routine of A. Spek has been performed. However, atomic co-ordinates for the “non-
SQUEEZE” structures are also presented. The tetrahedrally coordinated Zn is surrounded
by four linkers; one imidazole with 2-fold symmetry and one 2-nitroimidazole with
mirror symmetry have no disorder. The two remaining positions have both imidazole and
2-nitroimidazole as linkers, always with mirror symmetry. In one position the 2-
nitroimidazole occupancy is 29.8% and in the other position this occupancy is 44.2%.
The framework contains 1.13 imidazole and 0.87 2-nitroimidazole per Zn. It should be
noted that the precision of this model is low; however, the structure is reported to
describe the framework of ZIF-70 can be isolated in crystalline form. Other supporting
characterization data (vide infra Materials and Methods) agree with the crystal structure.
Final full matrix least-squares refinement on F2 converged to R1 = 0.0580 (F >2σF)) and
wR2 = 0.1944 (all data) with GOF = 1.129. For the structure where the SQUEEZE
program has not been employed, final full matrix least-squares refinement on F2
65
Empirical formula C6 H5.13 N4.87 O1.74 Zn

Space group P63/mmc
b = 27.0111(9) Å β = 90°
c = 18.0208(9) Å γ = 120°
Volume 11386.5(10)
Z 4
F(000) 3028
Crystal size 0.24 × 0.18 × 0.16 mm3
Index ranges -30 <= h <= 31, -31 <= k <= 30, -21 <= l <= 20
66
Empirical formula C6 H5.13 N4.87 O1.74 Zn

Space group P63/mmc
b = 27.0111(9) Å β = 90°
c = 18.0208(9) Å γ = 120°
Volume 11386.5(10)
Z 4
F(000) 2924
Crystal size 0.24 × 0.18 × 0.16 mm3
Index ranges -30 <= h <= 31, -31 <= k <= 30, -21 <= l <= 20
67
excluding the guest entities and the major component imidazole in the disordered
position.
Figure S19. ORTEP drawing of a zinc atom surrounded by four linkers of ZIF-70
excluding the guest entities and the minor component 2-nitroimidazole in the disordered
positions.
68
ZIF-71 (RHO─ CUBIC)
unique and 782 of these were greater than 2σ(I). The range of θ was from 1.55 to 36.83°.
in the cubic Pm-3m space group, with Z = 48, using direct methods. All non-hydrogen
coordinates of their parent atoms. Since absorption corrections (SADABS) were
ineffectual for improving the data quality of data this data has been processed without an
absorption correction. Modeling of electron density within the voids of the framework
did not lead to identification of guest entities in all structures due to the lowered
resolution of the data and a limited periodicity of the solvent molecules in the crystals.
Since the solvent is not bonded to the framework this can be expected for the MOF
structures. Many atomic co-ordinates that have been attributed to solvent molecules lie on
a special position. However, very high displacement parameters, high esd’s and partial
occupancy due to the disorder make it impossible to determine accurate positions for
these solvent molecules. Thus, electron density within void spaces which could not be
assigned to any definite guest entity was modeled as isolated carbon and oxygen atoms,
69
and the foremost errors in all the models lie with assignment of guest electron density. To
prove the correctness of the atomic positions in the framework the application of the
SQUEEZE routine of A. Spek has been performed. However atomic co-ordinates for the
“non-SQUEEZE” structures are also presented. The unit cell of ZIF-71 contains two 4,5-
dichloroimidazole per zinc. Final full matrix least-squares refinement on F2 converged to
R1 = 0.0424 (F >2σF)) and wR2 = 0.1045 (all data) with GOF = 1.022. For the structure
where the SQUEEZE program has not been employed, final full matrix least-squares
GOF = 1.073. When only framework atoms are included in the latter structure factor
calculation, the residual electron density in the F-map is located within the pores of ZIF-
71.
70
Empirical formula C7.30 H2 Cl4 N4 O0.03 Zn

Space group Pm-3m
b = 28.5539(2) Å β = 90°
c = 28.5539(2) Å γ = 90°
Volume 23280.7(3)
Z 48
F(000) 8259
Crystal size 0.22 × 0.20 × 0.19 mm3
Index ranges -22 <= h <= 22, -22 <= k <= 22, -22 <= l <= 22
Absorption correction None
71
Empirical formula C6 H2 Cl4 N4 Zn

Space group Pm-3m
b = 28.5539(2) Å β = 90°
c = 28.5539(2) Å γ = 90°
Volume 23280.7(3)
Z 48
F(000) 7872
Crystal size 0.22 × 0.20 × 0.19 mm3
Index ranges -22 <= h <= 22, -22 <= k <= 22, -22 <= l <= 22
Absorption correction None
72
entities.
73
ZIF-72 (LCS─ CUBIC)
in the cubic Ia-3d space group with Z = 2 using direct methods. Due to the low data to
parameter ratio atom C1 has been refined isotropically with the attached hydrogen atom
riding the coordinates of its parent atom. All other non-hydrogen atoms were refined
anisotropically. Absorption correction by SADABS decreases R(int) to 0.0235. The
absorption coefficient has a rather high value, μ = 10.268. A final ratio of 8.2 for
reflections to parameters was achieved. The unit cell of ZIF-72 reveals that the unit cell
contains two 4,5-dichloroimidazoles per zinc [Zn(45DCIM)2]. Final full matrix least-
with GOF = 1.185.
74
Empirical formula C6 H2 Cl4 N4 Zn

Space group Ia-3d
b = 19.6544(2) Å β = 90°
c = 19.6544(2) Å γ = 90°
Volume 7592.40(13)
Z 2
F(000) 3936.0
Crystal size 0.18 × 0.16 × 0.15 mm3
Index ranges -18 <= h <= 17, -17 <= k <= 18, -18 <= l <= 17
75
entities.
76
ZIF-73 (FRL─ Orthorhombic)
diameter nylon Cryo-Loops (Hampton Research) with Paraton-N (Hampton Research).
solved in the orthorhombic Ibam space group, with Z = 2, using direct methods. In the
framework two types of Zn occur in the ration of 4 to 1, both tetrahedrally linked to
imidazole via N. Zn(1) is surrounded by three 2-nitroimidazole linkers, but the fourth
position of the tetrahedron is occupied by either 2-nitroimidazole (35%) or 5,6
dimethylbenzimidazole (65%). Zn(2) is surrounded by four 2-nitroimidazole linkers. The
framework contains Zn, 2-nitroimidazole and 5,6-dimethylbenzimidazole in the ratio
1:1.74:0.26. Note that 5,6-dimethylbenzimidazole is found in only one position of the
framework. As a result N4, C7, C9, C10, and C11 have been refined anisotropically with
a 65% (X) site occupancy factor and atoms C14, N8, N17 and O18 have been refined
anisotropically with a 35% (1 – X) occupancy. All other non-hydrogen atoms were
refined anisotropically with hydrogen atoms generated as spheres riding the coordinates
of their parent atoms. Modeling of electron density within the voids did not lead to the
identification of a guest molecule. Many atomic co-ordinates that have been attributed to
77
solvent molecules lie on a special position. However, very high displacement parameters,
high esd’s and partial occupancy due to the disorder make it impossible to determine
accurate positions for these solvent molecules. Thus, electron density within void spaces
which could not be assigned to any definite guest entity was modeled as isolated carbon
and oxygen atoms, and the foremost errors in all the models lie with assignment of guest
electron density. To prove the correctness of the atomic positions in the framework the
application of the SQUEEZE routine of A. Spek has been performed. However, atomic
co-ordinates for the “non-SQUEEZE” structures are also presented. The unit cell of ZIF-
73 contains 0.26 5,6-dimethyl benzimidazole and 1.74 2-nitroimidazole per zinc. Final
full matrix least-squares refinement on F2 converged to R1 = 0.0322 (F >2σF)) and wR2 =
0.0882 (all data) with GOF = 1.115. For the structure where the SQUEEZE program has
not been applied, final full matrix least-squares refinement on F2 converged to R1 =
0.0396 (F >2σF)) and wR2 = 0.1185 (all data) with GOF = 1.146.
78
Empirical formula C75.60 H57 N57.40 O34.80 Zn10

Space group Ibam
b = 22.7960(4) Å β = 90°
c = 24.9704(5) Å γ = 90°
Volume 6242.1(2)
Z 2
F(000) 3186
Crystal size 0.29 × 0.16 × 0.12 mm3
Index ranges -12 <= h <= 12, -25 <= k <= 26, -28 <= l <= 28
79
Empirical formula C82.60 H57 N61.40 O38.80 Zn10

Space group Ibam
b = 22.7960(4) Å β = 90°
c = 24.9704(5) Å γ = 90°
Volume 6242.1(2)
Z 2
F(000) 2982
Crystal size 0.29 × 0.16 × 0.12 mm3
Index ranges -12 <= h <= 12, -25 <= k <= 26, -28 <= l <= 28
80
Figure S22. ORTEP drawing of an asymmetric unit of ZIF-73 excluding the guest
entities and the minor component 2-nitroimidazole. C8, N4, C7, C9, C11, and C10 are
part of the major component ligand, 5,6-dimethylbenzimidazole that links Zn1 atoms .
Figure S23. ORTEP drawing of an asymmetric unit of ZIF-73 excluding the guest
Entities and the major component ligand, 5,6-dimethylbenzimidazole. C8, N8, C14, and
N18 are atoms of the minor component ligand 2-nitroimidazole that links Zn1 atoms.
81
ZIF-74 (GIS─ Tetragonal)
A colorless prismic crystal (0.24 × 0.21 × 0.19 mm3) of ZIF-74 was placed in a 0.7 mm
solved in the tetragonal I41/a space group, with Z = 8, using direct methods. Atoms O1
and O2 were found to be disordered and were refined anisotropically with the occupancy
for each group modeled as its own independent free variable (X, 1 – X). All other non-
hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres
riding the coordinates of their parent atoms. It is probable that N5, which is bonded to the
disordered oxygen atoms O1 and O2, also could be modeled in two sites. However,
overlap for these N5 positions are too great and as a result N5 has been described as a
single atom with full occupancy (and consequently a rather high Ueq). C10, is expected
to have Ueq values similar to the rest of the five membered imidazole ring rather than
similar to the Ueq values for N5 of the NO2 ring. Modeling of electron density within the
voids of the frameworks lead to the identification of a DMF guest disordered about two
positions which has been refined isotropically with the hydrogen atoms for the CHO
functionality omitted. The unit cell of ZIF-74 contains one 5,6-dimethyl benzimidazole
82
and one 2-nitro imidazole (1:1) per zinc. Final full matrix least-squares refinement on F2
83

Space group I41/a
b = 16.6703(2) Å β = 90°
c = 21.6026(6) Å γ = 90°
Volume 6003.2(3)
Z 8
F(000) 2936
Crystal size 0.24 × 0.21 × 0.19 mm3
Index ranges -19 <= h <= 16, -16 <= k <= 18, -24 <= l <= 21
84
entities.
85
ZIF-75 (GIS─ Tetragonal)
A pink colored prismic crystal (0.24 × 0.21 × 0.19 mm3) of ZIF-75 was placed in a 0.7
mm diameter nylon Cryo-Loops (Hampton Research) with Paraton-N (Hampton
44.98°. Analysis of the data showed negligible decay during collection. However a high μ
= 9.195 and a low data to parameter ratio (6.08) is notable. The structure was solved in
the tetragonal I41/a space group, with Z = 4, using direct methods. Atoms O1 and O2
were found to be disordered and were refined isotropically with the occupancy for each
group modeled as its own independent free variable (X, 1 – X). All other non-hydrogen
frameworks does not lead to the identification of any guest molecule. Thus, electron
density within void spaces, which could not be assigned to any definite guest entity, was
modeled as isolated oxygen and carbon atoms, and the foremost errors in all the models
lies with assignment of guest electron density. The unit cell of ZIF-75 contains one 5,6-
dimethylbenzimidazole and one 2-nitroimidazole (1:1) per zinc. Final full matrix least-
with GOF = 1.037.
86

Space group I41/a
b = 16.6695(2) Å β = 90°
c = 21.5797(5) Å γ = 90°
Volume 5996.4(2)
Z 4
F(000) 2816
Crystal size 0.24 × 0.21 × 0.19 mm3
Index ranges -14 <= h <= 15, -14 <= k <= 15, -19 <= l <= 18
87
entities.
88
ZIF-76 (LTA─ Cubic)
solved in the cubic P-43m space group, with Z = 24, using direct methods. Although a
partial structural solution was found in space group Pm-3m but a better refinement was
achived in space group P-43m. All non-hydrogen atoms except zinc were refined
isotropically with hydrogen atoms generated as spheres riding the coordinates of their
parent atoms. The attempts made to model the guests (solvent molecules) did not lead to
identification of guest entities in all structures due to the limited periodicity of the solvent
molecules in the crystals. Since the solvent is neither bonded nor fits tightly in the
framework disordered solvent molecules can be expected for the MOF structures. Many
atomic co-ordinates that have been attributed to solvent molecules lie on a special
position. However, very high displacement parameters, high esd’s and partial occupancy
due to the disorder make it impossible to determine accurate positions for these solvent
molecules. Thus, electron density within void spaces which could not be assigned to any
definite guest entity has been modeled as isolated carbon and oxygen atoms, and the
89
foremost errors in all the models lie in the assignment of the guest electron density. ZIF-
76 is composed of 1.5 imidazole and 0.5 monochloro-benzimidazole per Zn. The larger
linker 5-chlorobenzimidazole occurs in two different linker positions, at half occupancy
in each. In these positions, the other half occupant is imidazole and the imidazole cycle
perfectly overlaps the imidazole moiety of the larger linker. The contents of the crystal
agree well with the elemental analysis of the bulk sample (3 imidazole and 1
chlorobenzimidazole tetrahedrally coordinated to a Zn atom). The benzimidazole must
have half occupancy (or less) because full occupancy in either position would require two
crystallographically related benzimidazole linkers to approach each other too closely. The
linkers in the remaining two positions are fully occupied by unsubstituted imidazole. The
framework is further complicated by a disorder involving three of the four linkers.
Rotation of 60 degrees about one of the N-Zn bonds (N1–Zn1) gives a second nitrogen
triangle involving the other three Zn-N bonds. Still another disorder results because the
chlorine atom of the chlorobenzene is randomly (50%) bonded to either of the two
possible ring carbon atoms. Three of the four imidazole positions are located about
mirror planes; two chlorine atom positions of an imidazole are related by mirror
symmetry, although of course only one of these positions is filled for any given
imidazole. It should be noted that the precision of this model is low; however, the
structure is reported to describe the ZIF-76 framework. Other supporting characterization
data (vide infra Materials and Methods) agree with crystal structure. To asses the
correctness of the atomic positions in the framework the application of the SQUEEZE
routine of A. Spek has been applied. However atomic co-ordinates for the “non-
SQUEEZE” structures are also presented. The unit cell of ZIF-76 contains 1.5 imidazole
90
and 0.5 5-chlorobenzimidazole imidazole per zinc. Final full matrix least-squares
GOF = 1.136. For the structure where the SQUEEZE program has not been employed,
final full matrix least-squares refinement on F2 converged to R1 = 0.1108 (F >2σF)) and
wR1 = 0.3072 (all data) with GOF = 1.542. When only framework atoms are included in
the latter structure factor calculation, the residual electron density in the F-map is located
within the pores of ZIF-76.
91
Empirical formula C7.69 H3.58 Cl0.42 N2.78ZN0.67

Space group P-43m
b = 22.6702(3) Å β = 90°
c = 22.6702(3) Å γ = 90°
Volume 11651.08(18)
Z 24
F(000) 3466
Crystal size 0.25 × 0.20 × 0.18 mm3
Index ranges -17 <= h <= 17, -17 <= k <= 17, -17 <= l <= 17
2
92
Empirical formula C5.83 H3.58 Cl0.42 N2.67

Space group P-43m
b = 22.6702(3) Å β = 90°
c = 22.6702(3) Å γ = 90°
Volume 11651.08(18)
Z 24
F(000) 3036
Crystal size 0.25 × 0.20 × 0.18 mm3
Index ranges -17 <= h <= 17, -17 <= k <= 17, -17 <= l <= 17
93
Figure S26. These figures depict two of the many Zn tetrahedron forms, each containing
3 imidazole linkers and 1 chlorobenzimidazole linker. Note that in one case Zn is
tetrahedrally surrounded by N1, N2, N3, and N4, and chlorobenzimidazole contains N1.
In the other figure, Zn is tetrahedrally surrounded by N1, N2’, N3’ and N4’, and
chlorobenzimidazole contains N2’. The imidazole containing N1 is present in both
figures, in one as chlorobenzimidazole and in the other as imidazole. Chlorine is present
in one of the two mirror-related positions.
94
ZIF-77 (FRL─ Orthorhombic)
A pink colorless cubic crystal (0.24 × 0.21 × 0.20 mm3) of ZIF-77 was placed in a 0.7
mm diameter nylon Cryo-Loops (Hampton Research) with Paraton-N (Hampton
54.23°. Analysis of the data showed negligible decay during collection. However a high μ
= 3.058 (because μ is based on atomic contents and this is uncertain because of the guest
this number is quite imprecise) and a rather low data to parameter ratio (8.23) should be
noted. The structure was solved in the orthorhombic Ibam space group, with Z = 2, using
direct methods. All non-hydrogen atoms in the framework were refined anisotropically
with hydrogen atoms generated as spheres riding the coordinates of their parent atoms.
Modeling of electron density within the voids of the frameworks leads to the
identification of one DMF as a guest molecule. However the other electron density within
void spaces, which could not be assigned to any definite guest entity, was modeled as
oxygen and carbon atoms, and the foremost errors in all the models lie with assignment
of guest electron density. The unit cell of ZIF-77 contains two 2-nitroimidazole links per
zinc. Final full matrix least-squares refinement on F2 converged to R1 = 0.0434 (F >2σF))
and wR2 = 0.1267 (all data) with GOF = 1.190.
95

Space group Ibam
b = 22.3469(12) Å β = 90°
c = 24.9087(14) Å γ = 90°
Volume 6192.4(6)
Z 2
F(000) 3224
Crystal size 0.24 × 0.21 × 0.20 mm3
Index ranges -11 <= h <= 11, -22 <= k <= 23, -26 <= l <= 22
96
entities.
97
Section S3. Thermal stability of ZIFs and the thermal gravimetric analysis
(TGA) data.
All samples were run on a TA Instruments Q-500 series thermal gravimetric
analyzer with samples held in platinum pans in a continuous flow nitrogen atmosphere.
Samples were heated at a constant rate of 5 °C/min during all TGA experiments.
Figure S28. The overlay of TGA traces of as-synthesized, solvent-exchanged, and
evacuated (activated) samples of ZIF-60.
The TGA traces of the as-synthesized ZIF-60 sample and the sample after being
immersed in dry methanol solvents at ambient temperature for three days are shown in
Figure S28. Clearly, treatment with dry methanol simplified the thermogravimetric
behavior of ZIF-60 significantly, indicative of effective solvent-exchange. In particular,
98
in the TGA trace of methanol-exchanged ZIF-60 sample, the initial gradual weight-loss
step of 34.3% till 100 °C were replaced by a small initial step (16.7% of weight loss ) at
100 °C temperature, a plateau to 550 °C and a sharp weight loss from that point onwards
indicates the decomposition of the material.
Figure S29. The overlay of TGA traces of as-synthesized and evacuated (activated)
samples of ZIF-61.
The TGA traces of as synthesized ZIF-61 sample. A flat plateau to 300 °C and a
very small weight loss (5.2%) indicated non-porous nature of the material. The as
synthesized sample was evacuated at room temperature for 10 hours to remove the
adhering DMF solvent from the surface. A flat plateau to 550 °C and the subsequent
decomposition of the material indicated the activation of the sample was complete.
99
The TGA traces of an as synthesized ZIF-68 sample and a sample after being
Figure S30. Clearly, treatment with methanol simplified the thermogravimetric behavior
of ZIF-68 significantly, indicative of effective solvent-exchange. In particular, in the
TGA trace of methanol-exchanged ZIF-68 sample, the original gradual weight-loss step
of 21.3% up to 168 °C was replaced by a small initial step (4.5%) at 118 °C temperature,
a plateau up to 400 °C and a sharp weight loss from that point onwards indicates the
decomposition of the material. The sample was activated by heating it at 85 °C under
vacuum for 72 hours. A flat plateau up till 400 °C and a subsequent decomposition of the
material indicated the activation of the sample was complete.
100
The TGA traces of as synthesized ZIF-69 sample and a sample after being
TGA trace of methanol-exchanged ZIF-69 sample, the original gradual weight-loss step
of 10.6% up to 164 °C was replaced by a small initial step (4.1%) at 80 °C temperature, a
plateau till 400 °C and a sharp weight loss from that point onwards indicates the
vacuum for 72 hours. A flat plateau to 400 °C and a subsequent decomposition of the
101
The TGA traces of an as synthesized ZIF-70 sample and a sample after being
TGA trace of a methanol-exchanged ZIF-70 sample, the original gradual weight-loss step
of 27.2% up to 170 °C were replaced by a small initial step (15.4%) at ambient
temperature (48 °C), a plateau till 350 °C and a sharp weight loss from that point onwards
indicates the decomposition of the material. The sample was activated by heating it at 85
°C under vacuum for 72 hours. A flat plateau to 350 °C and a subsequent decomposition
of the material indicated the activation of the sample was complete.
102
The TGA traces of as-synthesized ZIF-76 sample and a sample after being
TGA trace of a methanol-exchanged ZIF-68 sample, the original gradual weight-loss step
of 21.9% up to 164 °C were replaced by a small initial step (2%) at ambient temperature,
a plateau up to 550 °C and a sharp weight loss from that point onwards indicates the
vacuum for 72 hours. A flat plateau up till 550 °C and a subsequent decomposition of the
103
35000
30000
25000
20000
15000
10000
Activated
5000
Simulated
0
2 12 22 32
2 θ (degree)
Figure S34. PXRD patterns of activated and simulated ZIF-68. The PXRD pattern of the
activated sample has been collected after the sorption studies. Y-axis of the graph shows
the relative intensity.
104
14000
12000
10000
8000
6000
Activated
4000
2000 Simulated
0
2 12 22 32
2θ(degree)
105
25000
20000
15000
10000
Activated
5000
Simulated
0
2 12 22 32
106
Section S4. Chemical stability of ZIFs in refluxing organic and aqueous media and
the corresponding PXRD patterns.
ZIF-61, 68, 69, and 70 were tested for their stability in benzene, methanol and water.
These solvents were chosen to compare the relative effects of non-polar to polar solvents.
The tests were performed at room temperature, 50 °C and at the boiling point of each
solvent (methanol 65 °C, benzene 80 °C and water 100 °C) for up to 7 days. The
structural stability of the frameworks was monitored by aliquoting portions of the
samples for PXRD analysis after every 24 h period. These conditions generally reflect the
extreme operational parameters of typical industrial chemical processes. ZIF samples
were immersed in the desired solvent for 1–7 days at ambient temperature, 50 °C, and at
the boiling point of each medium. During this process, samples were periodically
observed under an optical microscope and found to be insoluble under each of these
conditions. PXRD patterns collected for each sample at designated intervals showed that
the solid samples of ZIF-61, 68, 69, and 70 maintained their full crystallinity and were
clearly impervious to the boiling organic solvents for 7 days. Hydrothermal stability of
ZIF-61, 68, 69, and 70 is superior to those of original MCM and SBA types of ordered
mesoporous silica. This exceptional resistance to hydrolysis is outstanding among metal–
organic solids. The plausible explanations for this type of resistance to hydrolysis can be
attributed to the hydrophobic pore and surface structure of ZIFs that likely repels water
molecules to attack ZnN4 units; and most stable bonding between IM and Zn(II)/Co(II)
among N-donor ligands (on the scale of metal-complex formation constants).
107
ZIF-61 Stability Test: Benzene at RT
25000
20000
15000 7 day
5 day
10000
3 day
5000 1day
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S37. PXRD patterns of ZIF-61 collected during stability test in benzene at room
temperature. The framework structure of ZIF-61 was unchanged after 7 days. Y-axis of
the graph shows the relative intensity.
108
ZIF-61 Stability Test: Benzene at 50 °C
30000
25000
7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S38. PXRD patterns of ZIF-61 collected during stability test in benzene at 50 °C.
The framework structure of ZIF-61 was unchanged after 7 days. Y-axis of the graph
shows the relative intensity.
109
30000
25000
7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S39. PXRD patterns of ZIF-61 collected during stability test in refluxing benzene.
110
ZIF-61 Stability Test: MeOH at RT
25000
20000
15000 7 day
5 day
10000
3 day
5000 1day
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S40. PXRD patterns of ZIF-61 collected during stability test in methanol at room
111
ZIF-61 Stability Test: MeOH at 50 °C
30000
25000
7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S41. PXRD patterns of ZIF-61 collected during stability test in methanol at 50
°C. The framework structure of ZIF-61 was unchanged after 7 days. Y-axis of the graph
112
30000
25000
7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S42. PXRD patterns of ZIF-61 collected during stability test in refluxing
methanol. The framework structure of ZIF-61 was unchanged after 7 days. Y-axis of the
graph shows the relative intensity.
113
ZIF-61 Stability Test: H2O at RT
25000
20000
15000 7 day
5 day
10000
3 day
5000 1day
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S43. PXRD patterns of ZIF-61 collected during stability test in water at room
114
ZIF-61 Stability Test: H2O at 50 °C
30000
25000
7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S44. PXRD patterns of ZIF-61 collected during stability test in water at 50 °C.
115
30000
25000
7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 2θ (degree) 32 42
Figure S45. PXRD patterns of ZIF-61 collected during stability test in refluxing water.
The framework structure of ZIF-61 was unchanged after 7 days. X-axis of the graph
116
18000
16000
14000 7 day
12000
5 day
10000
8000 3 day
6000
1day
4000
As Prepared
2000
0
2 12 22 2θ (degree) 32 42
117
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 32 42
2θ (degree)
The framework structure of ZIF-68 was unchanged after 7 days. X-axis of the graph
118
12000
10000 7 day
8000
5 day
6000
3 day
4000 1day
2000 As Prepared
0
2 12 22 32 42
2θ (degree)
119
18000
16000
14000 7 day
12000
5 day
10000
8000 3 day
6000
1day
4000
As Prepared
2000
0
2 12 22 2θ (degree) 32 42
120
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 32 42
2θ (degree)
121
12000
10000 7 day
8000
5 day
6000
3 day
4000 1day
2000 As Prepared
0
2 12 22 32 42
2θ (degree)
122
18000
16000
14000 7 day
12000
5 day
10000
8000 3 day
6000
1day
4000
As Prepared
2000
0
2 12 22 2θ (degree) 32 42
123
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 32 42
2θ (degree)
124
12000
10000 7 day
8000
5 day
6000
3 day
4000 1day
2000 As Prepared
0
2 12 22 32 42
2θ (degree)
125
16000
14000 7 day
12000
5 day
10000
8000 3 day
6000
1day
4000
2000 As Prepared
0
2 12 22 32 42
2θ (degree)
126
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 32 42
2θ (degree)
127
16000
7 day
14000
12000
5 day
10000
3 day
8000
6000
1day
4000
As Prepared
2000
0
2 12 22 32 42
2θ ( degree)
128
16000
14000 7 day
12000
5 day
10000
8000 3 day
6000
1day
4000
2000 As Prepared
0
2 12 22 32 42
2θ (degree)
129
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 32 42
2θ (degree)
130
ZIF-69 Stability Test: MeOH at 65°C
16000
7 day
14000
12000
5 day
10000
3 day
8000
6000
1day
4000
As Prepared
2000
0
2 12 22 32 42
2θ ( degree)
131
16000
14000 7 day
12000
5 day
10000
8000 3 day
6000
1day
4000
2000 As Prepared
0
2 12 22 32 42
2θ (degree)
132
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 32 42
2θ (degree)
133
16000
7 day
14000
12000
5 day
10000
3 day
8000
6000
1day
4000
As Prepared
2000
0
2 12 22 32 42
2θ ( degree)
134
45000
40000
35000
30000
25000 7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 32 42
2θ (degree)
135
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 2θ (degree) 32 42
136
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 2θ (degree) 32 42
137
45000
40000
35000
30000
25000 7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 32 42
2θ (degree)
138
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 2θ (degree) 32 42
139
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 2θ (degree) 32 42
140
45000
40000
35000
30000
25000 7 day
20000
5 day
15000
3 day
10000
1day
5000
As Prepared
0
2 12 22 32 42
2θ (degree)
141
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 2θ (degree) 32 42
142
10000
7 day
8000
5 day
6000
3 day
4000
1day
2000
As Prepared
0
2 12 22 2θ (degree) 32 42
143
Section S5. Porosity of ZIFs and carbon dixoide (CO2) selectivity and capacity
studies.
All low-pressure gas-sorption experiments (up to 1 atm) were performed on a
Quantachrome Autosorb-1 automatic volumetric instrument. In light of the TGA results
shown in the previous section, ZIF-68, 69, and 70 were evacuated in the following way
prior to gas-sorption analysis. The as-synthesized ZIF samples were immersed in dry
methanol at ambient temperature for 72 h, evacuated at ambient temperature for 24 h,
then at an elevated temperature (85 °C) for 48 h. ZIF samples thus obtained were
optimally evacuated, as evidenced by their well-maintained PXRD patterns and the long
plateau (ambient temperature to 350 °C) in their TGA traces, shown in Figures S30 and
S31 and S32.
The architectural rigidity and consequently the permanent porosity of evacuated
ZIF-68, 69, and 70 were unequivocally proven by gas-sorption analysis. Type I nitrogen
adsorption isotherm behavior was observed for all three of these ZIFs (Fig. 3A and S73),
which reveals its microporous nature. Apparent surface areas of 1,970 m2 g-1 (Langmuir
model, P/P0 = 0.06–0.30, the linearity of fitting 0.9999) and 1,730 m2 g-1 (Brunauer–
Emmett–Teller (BET) model [K. S. Walton, R. Q. Snurr, JACS 129, 8552 (2007)], P/P0 =
0.03–0.06, the linearity of fitting 0.9996) for ZIF-70 were obtained by using the data
points on the adsorption branch. Similarly, apparent surface areas of 1,220 m2 g-1
(Langmuir model, P/P0 = 0.04–0.30, the linearity of fitting 0.9999) and 1,090 m2 g-1
(BET model, P/P0 = 0.01–0.04, the linearity of fitting 0.9999) for ZIF-68, and 1,070 m2
g-1 (Langmuir model, P/P0 = 0.07–0.30, the linearity of fitting 0.9999) and 950 m2 g-1
(BET model, P/P0 = 0.01–0.04, the linearity of fitting 0.9997) for ZIF-69 were obtained
144
by using the data points on the adsorption branch respectively. These surface areas
surpass the highest values reported for zeolites, mesoporous silicas (MCMs, SBAs) and
ZIFs reported so far.
500
450
400
350
Uptake cm3/g STP
300
250
200 ZIF-70 N2 Adsorption

ZIF-70 N2 Desorption
150 ZIF68 N2 Adsorption
ZIF 68 N2 Desorption
100
ZIF69 N2 Adsorption
50 ZIF69 N2 Desorption
0
-0.05 0.05 0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95
P/P0
Figure S73. The N2 gas-sorption isotherms for prototypical ZIF-68, 69, and 70 measured
at 77 K. The filled and open circles represent adsorption and desorption branches,
respectively. STP represents standard temperature and pressure.
145
CO2 and CO isotherms of ZIF-68, 69, and 70 at room temperature (273 K) are
shown below in Figure S74-S76. A nice fitting of each CO2 isotherm adsorption branch
has been calculated based on Toth’s isotherm model (Figure S77-S82).
Toth Model: M = Mmax·B(1/n)·P/(1 + B × P)1/n……………………….(1)
M, gas uptake (mmol/g); Mmax, maximum gas uptake (mmol/g); B and n, fitting
constants; Henry’s law constant K = dN = B1/ n ⋅ M max …………………….(2)

dP
P →0
Henry’s law selectivity (upper limit selectivity), gas component i over j Sij
Si,j = Ki/Kj……………………………………………………………...(3)
146
Figure S74. The CO2 (red) and CO (black) gas-sorption isotherms for prototypical ZIF-
68 at 273 K. The filled and open circles represent adsorption and desorption branches,
respectively. The CO2 uptake at 760 torr is higher than that of CO suggesting a stronger
interaction between the framework and the CO2 molecules.
147
respectively. The CO2 uptake at 760 torr is eight times higher than that of CO suggesting
a stronger interaction between the framework and the CO2 molecules.
148
respectively. The CO2 uptake at 760 torr is eight times higher than that of CO suggesting
a stronger interaction between the framework and the CO2 molecules.
149
ZIF-68 CO2
B = 0.01607
Mmax = 17.74
n = 0.5462
X2 = 5.809×10-4
K = 7.010 mmol g-1 atm-1
Figure S77. CO2 isotherm adsorption branch of ZIF-68 (red filled circles) and fitting
based on Toth isotherm model (red open circles); Mmax, maximum uptake; B and n, fitting
constants; X2 fitting error; K, Henry’s law constant.
150
ZIF-68 CO
B = 0.001541
Mmax = 20.65
n = 0.6069
X2 = 1.717×10-6
K = 0.3648 mmol g-1 atm-1
Figure S78. CO isotherm adsorption branch of ZIF-68 (red filled circles) and fitting
151
ZIF-69 CO2
B = 0.006563
Mmax = 10.22
n = 0.7113
X2 = 2.579×10-4
K = 6.625 mmol g-1 atm-1
152
ZIF-69 CO
B = 0.001581
Mmax = 17.78
n = 0.6051
X2 = 5.968×10-6
K = 0.3176 mmol g-1 atm-1
153
ZIF-70 CO2
B = 0.08928
Mmax = 525.7
n = 0.2288
X2 = 7.516 ×10-4
K = 10.41 mmol g-1 atm-1
154
ZIF-70 CO
B = 0.003418
Mmax = 8.226
n = 0.5661
X2 = 3.891 ×10-6
K = 0.2751 mmol g-1 atm-1
155
The gas-separation property of ZIF-68, 69, and 70 were tested by breakthrough
experiments (see Figure S86 for schematic representation of the separation apparatus)
using a CO2/CO (about 50:50 v/v) gas mixture. 1.1 g of activated ZIF-68, 1.4 g of
activated ZIF-69 and 1.2 g of activated ZIF-70 were packed into a stainless-steel column
(0.46 inner-diameter and 8 cm length) in a glove box respectively. The columns were
then attached to gas-separation apparatus built as shown in Figure S86. Helium gas was
initially purged into the sample columns. All the experiments were carried out at room
temperature. The gases (20 psi) were premixed in 1:1 ratio and dosed into the column at a
flow rate of 20 mL min−1. The relative amounts of the gases passing through the column
were monitored on a Hiden Analytical HPR20 gas analysis system detecting ion peaks at
m/z+ 44 (CO2) and 12 (CO) (see Figures S83-S85). The relative intensity of each gas
component was normalized to the same level when purging gas mixtures through bypass
before they passed through the column.
156
Relative intensity
CO
CO2
0 50 100 150 200 250 300 350 400

Time (s)
Figure S83. Breakthrough curves of CO2 (blue) and CO (black) for ZIF-68 using a
CO2/CO gas mixture. ZIF-68 has not only a permanent porosity, but also shows gas-
separation ability. The relative intensities of each gas passing through the ZIF-68-packed
column were obtained using a mass spectrometer to detect ion peaks at m/z+ = 44 (CO2)
and 12 (CO).
157
Relative intensity
CO
CO2
0 0.5 1 1.5 2 2.5 3 3.5

Time (m)
and 12 (CO).
158
Relative intensity
CO
CO2
0 20 40 60 80 100 120 140 160 180 200

Time (s)
and 12 (CO).
159
Gas Separation/Breakthrough Manifold:
Mass Spec Detector
v3 v4 v5 vent
f1 f2 f3 v6
c1
g1a g2a g1b g2b g1c g2c
v1a v1b v1c PC
v7
v2a v2b v2c HIDEN Gas
MS
Mass Spec samples continuously from effluent stream; 1-4 data

Gas 1 Gas 2 Gas 3 points/minute
Allows for detection of “IR-invisible” materials, e.g. Cl2
V6, V7 switch between sample cell c1 and bypass tube to
establish baseline signal, calibrate concentration measurement
via software
v = valve
f = flowmeter (rotameter)
g = pressure gauge
c = sample cell
Figure S86. Schematic representation of gas separation/breakthrough apparatus.
160

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Supporting Online Material for

*To whom correspondence should be addressed.

Published 15 February 2008, Science 319, 939 (2008)

This PDF file includes:

High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and

Rahul Banerjee1*, Anh Phan1, Bo Wang1, Carolyn Knobler1, Hiroyasu Furukawa1,

Michael O’Keeffe2, Omar M. Yaghi1*

Detailed synthesis procedures for ZIFs including multi-gram scale

Representative optical photographs of ZIFs crystals (0.1 to 1 mm) and

Thermal stability of ZIFs and the thermal gravimetric analysis (TGA)

Chemical stability of ZIFs in refluxing organic and aqueous media and

Porosity of ZIFs and carbon dioxide (CO2) selectivity and capacity

General Synthetic Procedures: Benzimidazole, 2-methylimidazole, 2-ethylimidazole,

Aldrich Chemical Co. and imidazole, N,N-dimethylformamide (DMF), N-

2-nitroimidazole was purchased from 3B Scientific Corporation. N,N-diethylformamide

experimental operations were performed in air.

The fully integrated high throughput synthetic apparatus consists of a number of

components, including experimental design and execution software, robotic dispensing

structural interpretation. All ZIFs were synthesized by using this combinatorial

us to use 0.300 mL reactant volume per well. A solution of imidazole(s) in DMF/DEF

(0.075–0.20 M) and a solution of a hydrated metal salt (usually nitrate) in DMF/DEF

an automated optical microscope, isolated, and characterized by single-crystal x-ray

diffraction. The isolation of the sample array is accomplished in parallel by sonication

phase or it falls in the category of the ZIFs published already.

single crystal data.

with the unit cell dimensions of ZIF-2 previously reported.

cell dimensions of ZIF-4 previously reported.

(ZIF-8 sod): Zn(mIM)2. To a 0.225 mL 2-methylimidazole stock solution (0.20 M, 4.5 ×

cell dimensions of ZIF-8 previously reported.

dimensions of ZIF-10 previously reported.

dimensions of ZIF-11 previously reported.

dimensions of ZIF-12 previously reported.

(ZIF-14 ana): Zn(eIM)2. To a 0.20 mL 2-ethylimidazole stock solution (0.20 M, 4.0 ×

cell dimensions of ZIF-20 previously reported.

cell dimension of ZIF-21 previously reported previously reported.

of prism-shaped single crystals.

Elemental analysis C13H9N8Zn2 = Zn(IM)1.5(MeIM)0.5·(Me2NH)(H2O)3: Calcd. C, 33.17;

H, 6.55; N, 22.76. Found C, 33.28; H, 6.19; N, 22.13.

Elemental analysis (activated) C13H9N8Zn2 = Zn(IM)1.5(MeIM)0.5: Calcd. C, 37.44; H,

1602(m), 1505(w), 1250(w), 1163(w), 955(w), 756(w), 675(w).

structure as the single crystal.

shaped single crystals.

Elemental analysis C7H9N4Zn = Zn(IM)(MeIM): Calcd. C, 38.99; H, 3.74; N, 25.99; Zn,

30.34. Found C, 39.17; H, 3.39; N, 26.13; Zn, 29.98.

1499(m), 1474(w), 1316(w), 1174(w), 1008(w), 837(w), 675(w), 420(s).

structure as the single crystal.

prism-shaped single crystals.

(ZIF-65 sod): Co(nIM)2. To a 0.25 mL 2-nitroimidazole stock solution (0.20 M, 5.0 ×

(ZIF-68 gme): Zn(nIM)(bIM). 0.180 mL 2-nitroimidazole stock solution (0.20 M, 3.6 ×

yellow colored prism-shaped single crystals.

Elemental analysis C10H9N5O2Zn = Zn(NO2IM)(PhIM)·(DMF)(H2O)2: Calcd. C, 36.10;

H, 3.33; N, 21.05. Found C, 35.47; H, 2.89; N, 21.83.

Elemental analysis (activated) C10H9N5O2Zn = Zn(NO2IM)(PhIM): Calcd. C, 40.49; H,

2523(m), 2319(w), 1678(w), 1479(w), 1367(w), 1245(w), 1174(w), 909(s), 741(w),

structure as the single crystal.

(ZIF-69 gme): Zn(nIM)(5cbIM). 0.12 mL 2-nitroimidazole stock solution (0.20 M, 2.4

of yellow colored prism-shaped single crystals.