Pore surface engineering with controlled loadings of functional groups via click chemistry in highly stable metal-organic frameworks

Article abstract of DOI:10.1021/ja3063919

Reactions of ZrCl₄ and single or mixed linear dicarboxylic acids bearing methyl or azide groups lead to highly stable isoreticular metal-organic frameworks (MOFs) with content-tunable, accessible, reactive azide groups inside the large pores. T

Full text of DOI:10.1021/ja3063919

Subscriber access provided by UNIV OF CALGARY
Communication
Pore Surface Engineering with Controlled Loadings of Functional
Groups via Click Chemistry in Highly Stable Metal-Organic Frameworks
Hai-Long Jiang, Dawei Feng, Tian-Fu Liu, Jian-Rong (Jeff) Li, and Hong-Cai (Joe) Zhou
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja3063919 • Publication Date (Web): 20 Aug 2012
Downloaded from http://pubs.acs.org on August 24, 2012
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Pore Surface Engineering with Controlled Loadings of Func-
tional Groups via Click Chemistry in Highly Stable Metal-
Organic Frameworks
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Hai-Long Jiang, Dawei Feng, Tian-Fu Liu, Jian-Rong Li, and Hong-Cai Zhou*
Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842, USA
Supporting Information Placeholder
amine or carboxylic acid group, which significantly limits the
ABSTRACT: Reactions of ZrCl4 and single or mixed linear di-
carboxylic acids bearing methyl or azide groups lead to highly
utility of the approach.9 Hupp and Nguyen groups, Farrusseng and
coworkers have also applied click reactions in PSM of MOFs,
stable isoreticular metal-organic frameworks (MOFs) with con-
where very careful deprotection of acetylene group or transfor-
tent-tunable, accessible, reactive azide groups inside the large
mation of amine to azide group is a necessary step prior to a click
pores. These Zr-based MOFs offer an ideal platform for pore sur-
reaction.10 Multiple steps in PSM often cause partial or complete
face engineering of anchoring various functional groups with
framework collapse, especially when the MOF is not robust. In
controlled loadings onto pore walls via click reaction, endowing
addition, grafting functional groups with controlled loadings in
MOFs with tailor-made interfaces. Significantly, the framework
MOFs has not yet been achieved. Herein we report the preparation
and crystallinity of functionalized MOFs are well retained, and
of highly stable isoreticular Zr-based MOFs with accessible, reac-
the engineered pore surfaces have been demonstrated to be readily
tive azide groups in large pores, which enable the MOFs to un-
accessible, thus bringing more opportunities for powerful and
dergo a quantitative click reaction with alkynes to form triazole-
broad applications of MOFs.
linked groups on the pore wall surfaces. Significantly, our syn-
thetic route allows an accurate control of the loading of azide
groups on the internal surface of the MOF for the first time. The
highly stable Zr-based MOFs offer an ideal platform for pore
As highly ordered porous materials, metal-organic frameworks
surface engineering. A variety of functional groups can be an-
(MOFs) have attracted great interest in the last twenty years due
chored onto pore walls in MOFs with precise control over the
to their crystalline nature, pore tunability and structural diversity,
as well as numerous potential applications such as gas stor-
loading, density, and functionalities.
age/separation, catalysis, sensing and drug delivery.1-5 Permanent
porosity and chemical environment of the internal surface of
MOFs are crucial for such applications. However, pore surface
modification with desired functional groups in well-defined
MOFs remains a significant challenge. Currently, the modification
of MOF pore surfaces is mostly based on the pre-designed ligand
with a specific functional group.6 This approach is somewhat
limited owing to the cumbersome multistep process of ligand
synthesis and the often unpredictable coordination between reac-
tive functional groups (such as, -OH, -COOH, N-donating groups,
etc.) and metal centers during the MOF assembly process. Moreo-
ver, it is generally difficult to obtain MOFs with long and/or large
groups appended on the pore walls by direct solvothermal reac-
tions. Therefore, the development of a general strategy for sys-
tematic pore surface engineering of MOF pore walls is impera-
tive, which would endow MOFs with a tailor-made internal sur-
face to meet specific application requirements.
Figure 1. (a) View of the structure of PCN-56 as a representative,
bearing two methyl groups in each TPDC-derived linker. Accord-
ingly, four methyl, two methyl azide, and four methyl azide
Postsynthetic modification (PSM) represents a powerful tool
to anchor functional groups onto MOFs. For instance, Cohen and
coworkers have employed MOFs bearing -NH2 groups as plat-
forms to graft various functional groups such as aldehydes, isocy-
anates, and anhydrides.7 Recently, Sharpless click chemistry has
also been demonstrated to be an alternative route to enrich the
chemical diversity of MOFs.8-10 Sada and coworkers have em-
ployed a Zn-based MOF bearing azide groups for PSM applying
the click chemistry, although the MOF dissolves when soaking in
a solution with “reactive” molecules, such as reactants bearing an
groups are involved in each organic linker, respectively for PCN-
57, PCN-58 and PCN-59. Inset: the Zr6 cluster. (b) Tetrahedral
and (c) octahedral cages comprised Zr6 clusters and organic link-
ers in PCN-56. The cavities are highlighted with green spheres.
To design an azide-appended MOF material with large enough
cavities whose openings can be fully accessed by various mole-
cules with alkyne group for click reaction, we designed four elon-
gated linear dicarboxylic acids with three benzene rings in each,
2',5'-dimethyl-terphenyl-4,4''-dicarboxylic acid (TPDC-2CH3) and
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
2',3',5',6'-tetramethyl-terphenyl-4,4''-dicarboxylic acid (TPDC-
(3D) network with two types of polyhedral cages (Figure 1a). One
1
2
3
4
5
6
7
8
4CH3), as well as their corresponding azide derivatives (TPDC-
2CH2N3 and TPDC-4CH2N3), as organic linkers (Supporting In-
formation, Section 2). To ensure the structural integrity during
click reaction, we aimed to construct Zr-based MOFs, which are
well-known for their superior stability to the common Zn/Cu-
centered MOFs.11 It is especially difficult to obtain single crystals
of Zr-based MOFs due to the inert coordination bonds between
Zr4+ cations and carboxylate anions, making ligand exchange
reactions extremely slow, which is unfavorable for defects repair
during crystal growth.11 To overcome this difficulty, modulated
synthetic strategy was adopted and benzoic acid was introduced to
the synthetic system.11c To our delight, octahedron-shaped crys-
tals suitable for single crystal X-ray diffraction studies have been
obtained from a reaction mixture containing zirconium(IV) chlo-
ride, the elongated organic linkers, benzoic acid, and DMF, which
was allowed to stay at 100 ºC in an oven for 2 days (or 120 ºC for
12-18 h) (Supporting Information, Section 3 and Figure S40).12
Four MOFs, Zr3O2(OH)2(TPDC-R)3 (R = -2CH3, PCN-56; -4CH3,
PCN-57; -2CH2N3, PCN-58; -4CH2N3, PCN-59. PCN represents
porous coordination networks), have been confirmed to possess
isoreticular structures, which are similar to the UiO type struc-
tures, based on single crystal X-ray structural and powder X-ray
diffraction (PXRD) analyses (Supporting Information, Sections 4
and 5).11a In the absence of benzoic acid, these MOFs can also be
obtained but only in fine powders, revealing the vital role of ben-
zoic acid for the growth of crystals (Figure S45). Characteristic
infrared (IR) band of azide group (at ~2100 cm-1) is absent for
PCN-56 and -57 whereas it is stronger for PCN-59 than that for
PCN-58, consistent with the suggested structures. Moreover, di-
gested PCN-58 and -59 crystals in DMSO afford almost the same
1H NMR spectra as those of the corresponding organic linkers,
further demonstrating the intactness of ligand in the MOFs (Fig-
ure S25).
is tetrahedral comprising three Zr6 clusters and six ligands with a
cavity diameter of ~1.1 nm (Figure 1b), the other is octahedral
with a cavity diameter of ~2.2 nm surrounded by six Zr6 clusters
and twelve ligands (Figure 1c).
Zr6
Zr6
Zr6
Zr6
Zr6
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Zr6
Zr6
Zr6
Zr6
Zr6
Figure 3. Schematic illustration for the general strategy of pore
surface engineering of MOFs with precise control over the com-
position, density and functionalities by two steps in current syn-
thetic system: 1) introducing azide group with a desired loading
into the MOF (any value from 0 to 100%) by simply changing the
molar ratio of methyl- and azide-appended ligands only; 2) vari-
ous functional groups are grafted onto the pore walls of MOFs via
click reaction between azide and alkyne groups in quantitative
yield. The green spheres represent Zr6 clusters.
With strong bonds between the Zr4+ cation and the O atoms
thanks largely to the high charge density (Z/r) and the consequen-
tial bond polarization, all these MOFs exhibit exceptional robust-
ness. Thermal gravimetric analyses indicate that PCN-58 and -59
with methyl groups are stable up to 350-400 ºC, while frame-
works of PCN-58 and -59 bearing azide group remain intact over
200 ºC, after which the decomposition of the azide groups triggers
the collapse of the whole framework. Importantly, chemical sta-
bility examinations reveal that these MOFs not only survive water
treatment but also remain intact in dilute acid (pH = 2 solution
with HCl) and base (pH = 11 solution with NaOH) for some time
(Supporting Information, Section 12).
1000
(a)
800
(b)
(c)
600
Given the microporosity and robustness, all of the MOFs dis-
play typical type-I gas sorption isotherms with a range of surface
areas, in which PCN-56 presents BET surface area as high as
3741 m2/g (Figure 2). Although PCN-58 and -59 have decreased
surface areas due to the occupied pores by azide groups, the intro-
duction of azide group improves the adsorption enthalpy of CO2
(20, 22, 25 and 33 kJ/mol respectively for PCN-56 to -59) and
effectively enhances CO2 capture performance because of the
polarity of azide groups.
(d)
400
200
0
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P/P0)
The loading of azide groups on the pore walls can be accurately
tuned by varying the ratio of ligands with and without azide
groups during the MOF synthesis. Based on the current study and
literature reports, it is evident that appending azide groups to the
linker does not change the final MOF structure.6b,13 Hence, it is
reasonable to assume that pre-adjusting the molar ratio of TPDC-
CH3 : TPDC-CH2N3 will allow the control of azide loading in the
resultant MOFs. To test this hypothesis, MOFs with 25% and
75% -N3 loadings have been obtained by employing 1:1 of TPDC-
2CH3 and TPDC-2CH2N3, and 1:1 of TPDC-2CH2N3 and TPDC-
4CH2N3 ligands, respectively (Figure 3). These MOFs show
PXRD patterns similar to those of PCN-56 to -59, indicating the
retention of the framework structure. They also have similar IR
features but the intensity and peak area of the azide absorption
band at ~2100 cm-1 almost linearly increase as the azide loading
become higher (Figure 4), together with elemental analysis re-
sults, further demonstrating the consistency between theoretical
Figure 2. N2 sorption properties for (a) PCN-56, (b) PCN-57, (c)
PCN-58, and (d) PCN-59 at 77 K and 1 atm. Solid circles or
squares: adsorption; open: desorption. The BET surface areas are
3741, 2572, 2185 and 1279 m2/g, respectively for PCN-56 to -59,
which are comparable to calculated values (3317, 2416, 2131 and
1168 m2/g, respectively for PCN-56 to -59).
All MOFs crystallize in the Fm-3m space group and the unique
Zr atom, in a square-antiprismatic coordination environment, is
coordinated by eight oxygen atoms from four carboxylates and
four µ3-O and µ3-OH groups. Six Zr atoms are interconnected by
O atoms to form a Zr6O4(OH)4 octahdedral core, the triangular
faces of which are alternatively capped by µ3-O and µ3-OH groups
(Figure 1a, inset). All of the polyhedron edges are bridged by
carboxylates from the ligands to afford a Zr6O4(OH)4(CO2)12 clus-
ter. Each cluster is connected by twelve linear ligands and each
linear ligand links two clusters giving rise to a three-dimensional
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
and actual contents of azide groups in MOFs (Supporting Infor-
assembly with mixed ligands may be general. It will allow us to
1
2
3
4
5
6
7
8
mation, Section 11). This remarkable synthetic strategy can be
further extended to the synthesis of other isoreticular MOFs with
any azide loadings between 0 and 100% under similar reaction
conditions by simply adjusting the ligand ratio. Most importantly,
if coupled with postsynthetic click reaction such a synthetic strat-
egy of MOF functionalization via co-assembly with mixed ligands
provides a universal pathway toward MOFs with desired internal
surface properties, which are vital for their applications.
anchor almost any desired functional groups with precisely con-
trolled loadings onto pore walls in MOFs, thus to realize more
potential applications.
1.0
0.8
0.6
0.4
0.2
0.0
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 4. IR spectra of Zr-MOFs with (a) 0% N3 (PCN-56), (b)
25% N3, (c) 50% N3 (PCN-58), (d) 75% N3, and (e) 100% N3
(PCN-59). The characteristic IR band (highlighted with light pur-
ple background) for azide group is at ~2100 cm-1. The intensity of
this band is proportional to the azide loading of each MOF.
Figure 5. Normalized CO2 adsorption selectivity over N2 (ob-
tained from CO2 sorption amount (1 atm and 273 K for red bars; 1
atom and 296 K for blue bars) divided by N2 sorption amount at 1
atm and 77 K) for three sets of samples (Zr-MOFs with various
loadings of azide group, black marks; hydroxyl group anchored
onto Zr-MOFs with various loadings of azide group, green marks;
and diverse functional group anchored onto PCN-58, blue marks).
The Zr-MOFs with various azide loadings (25%, 50%, 75% and
100%) were allowed to react with propargyl alcohol in the pres-
ence of CuI as a catalyst at 60 ºC in DMF. After the reaction was
terminated, the products were isolated by centrifugation and
washed with acetone to afford products in quantitative yields. It
was demonstrated that very few Cu species (< 2 wt%) from the
CuI catalyst remained in the product (Supporting Information,
Section 14), similar to the previous report.14 PXRD studies con-
firmed the retention of the framework integrity and the crystallini-
ty of the resultant Zr-MOFs, which are now anchored by various
loadings of hydroxyl groups (Supporting Information, Section
13). As the direct evidence of a complete click reaction, the char-
acteristic IR band for the azide group disappeared completely
(Supporting Information, Sections 8 and 10).
Upon the introduction of diverse functional groups that may
have different affinities to specific gas molecules, the selective
sorption capability of the resultant MOFs can be tuned. As a
proof-of-concept study, we focused on the selective sorption of
CO2 over N2, which is critical for carbon capture from air or flue
gas stream. Compared to the MOF precursors, all functionalized
MOFs exhibit moderate BET surface area (400-1000 m2/g for
PCN-58-derived products and 200-450 m2/g for PCN-59 derived
products) after click reaction (Table 1), indicative of space filling
by the functional groups introduced. Their N2 uptake at 273 K is
almost undetectable, while they can adsorb significant amount of
CO2 at 273 or 296 K and 1 atm (Supporting Information, Sections
8 and 10). As shown in Figure 5, it is evident that the introduction
of azide groups increases the selectivity of CO2 over N2 (vide
supra). Different loadings of azide groups in the MOF enable us
to anchor the corresponding amounts of hydroxyl group onto the
pore walls. Overall, the selectivity of CO2 over N2 is also propor-
tional to the loadings of the hydroxyl groups. In addition, various
functional groups embedded into PCN-58 result in different selec-
tivity of CO2 over N2, in which amine is the functional group that
shows the highest selectivity due to the presence of not only po-
larity interaction but also “acid-base” reaction between alkyla-
mine and CO2 molecules, which is in agreement with previous
reports.15 In summary, preliminary results have revealed that pore
surface engineering of MOFs with diverse groups and controlled
loading significantly affect their gas sorption selectivity.
Given that various functional groups inside the pores will en-
dow MOFs with distinct and novel properties, it is highly desira-
ble to introduce a variety of functional groups into MOFs by
postsynthetic click reaction. Bearing this in mind, we further in-
vestigated click reactions of PCN-58 and -59 with other alkynes
involving various groups, such as propargyl acetate, methyl pro-
piolate, propargylamine, phenylacetylene, and propiolic acid.
Under reaction conditions similar to those for propargyl alcohol,
various functional groups have been successfully anchored onto
the MOF pore walls via a triazole linkage by click reaction. Here-
in, the positions and loadings of the functional groups are identi-
cal to those of the azide-appended MOF precursors. The identity
of the functionalized MOFs is validated by PXRD and IR charac-
terizations. To further verify the proposed products via click reac-
1
tion, we investigated the H NMR spectra of the digested solu-
Table 1. Experimental BET Surface Areaa (m2/g) for
MOFs Bearing Different Contents of N3 Group that Func-
tionalized with Diverse Groups and Different Loadings via
Click Reactions.
tions for all PCN-58-derived products; the results illustrated that
the corresponding triazole derivatives were formed and almost no
starting material was observed (Supporting Information, Section
8). Based on the above studies, the coupled strategy of postsyn-
thetic click reaction and MOF functionalization through co-
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
132, 5586. (c) Takashima, Y.; Martinez, V.; Furukawa, S.; Kondo, M.;
Group
OH
OCOMe COOMe NH2 phenyl COOH
Shimomura, S.; Uehara, H.; Nakahama, M.; Sugimoto, K.; Kitagawa, S.
Nat. Commun. 2011, 2, 168. (d) Kreno, L. E.; Leong, K.; Farha, O. K.;
Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105.
(5) (a) An, J.; Geib, S. J.; Rosi, N. L. J. Am. Chem. Soc. 2009, 131,
8376. (b) Rocca, J. D.; Liu, D.; Lin, W. Acc. Chem. Res. 2011, 44, 957. (c)
Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.;
Férey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232.
(6) (a) Devic, T.; Horcajada, P.; Serre, C.; Salles, F.; Maurin, G.; Mou-
lin, B.; Heurtaux, D.; Clet, G.; Vimont, A.; Grenèche, J.-M.; Le Ouay, B.;
Moreau, F.; Magnier, E.; Filinchuk, Y.; Marrot, J.; Lavalley, J.-C.; Daturi,
M.; Férey G. J. Am. Chem. Soc. 2010, 132, 1127. (b) Deng, H.; Doonan,
C. J.; Furukawa, H.; Ferreira, R. B.; Towne, J.; Knobler, C. B.; Wang, B.;
Yaghi, O. M. Science 2010, 327, 846. (c) Biswas, S.; Ahnfeldt, T.; Stock,
N. Inorg. Chem. 2011, 50, 9518.
(7) (a) Wang, Z.; Cohen, S. M. J. Am. Chem. Soc. 2007, 129, 12368.
(b) Cohen, S. M. Chem. Rev. 2012, 112, 970.
(8) (a) Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int.
Ed. 2001, 40, 2004.
(9) Goto, Y.; Sato, H.; Shinkai, S.; Sada, K. J. Am. Chem. Soc. 2008,
130, 14354.
(10) (a) Gadzikwa, T.; Lu, G.; Stern, C. L.; Wilson, S. R.; Hupp, J. T.;
Nguyen, S. T. Chem. Commun. 2008, 5493. (b) Gadzikwa, T.; Farha, O.
K.; Malliakas, C. D.; Kanatzidis, M. G.; Hupp, J. T.; Nguyen, S. T. J. Am.
Chem. Soc. 2009, 131, 13613. (c) Savonnet, M.; Bazer-Bachi, D.; Bats,
N.; Perez-Pellitero, J.; Jeanneau, E.; Lecocq, V.; Pinel, C.; Farrusseng, D.
J. Am. Chem. Soc. 2010, 132, 4518. (d) Savonnet, M.; Kockrick, E.; Ca-
marata, A.; Bazer-Bachi, D.; Bats, N.; Lecocq, V.; Pinela, C.; Farrusseng,
D. New J. Chem. 2011, 35, 1892. (e) Savonnet, M.; Camarata, A.; Canivet,
J.; Bazer-Bachi, D.; Bats, N.; Lecocq, V.; Pinela, C.; Farrusseng, D. Dal-
ton Trans. 2012, 41, 3945.
(11) (a) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti,
C.; Bordiga, S.; Lillerud, K. P. J. Am. Chem. Soc. 2008, 130, 13850. (b)
Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye, U.; Tilset,
M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P. Chem. Mater.
2010, 22, 6632. (c) Schaate A.; Roy, P.; Godt, A.; Lippke, J.; Waltz, F.;
Wiebcke, M.; Behrens, P. Chem. Eur. J. 2011, 17, 6643. (d) Schaate, A.;
Roy, P.; Preuße, T.; Lohmeier, S. J.; Godt, A.; Behrens, P. Chem. Eur. J.
2011, 17, 9320. (e) Morris, W.; Volosskiy, B.; Demir, S.; Gándara, F.;
McGrier, P. L.; Furukawa, H.; Cascio, D.; Stoddart, J. F.; Yaghi, O. M.
Inorg. Chem. 2012, 51, 6443.
1
2
3
4
5
6
7
8
25% N3
50% N3
75% N3
1409
845
848
427
-
-
-
-
-
b
907
-
405
-
595
-
721
-
560
-
c
100% N3
342
200
404
220
293
aDecided by 0.005 < P/P0 < 0.15. bi. e. PCN-58. ci. e. PCN-59.
In conclusion, reactions of ZrCl4 and single or mixed linear lig-
ands bearing methyl or azide groups lead to highly stable isoretic-
ular Zr-MOFs with tunable loadings of azide group inside the
pores. For the first time, the system offers an ideal platform for
facile pore surface engineering by introducing various functional
groups with controlled loadings via click reaction. Remarkably,
the resultant click products have been demonstrated to possess
well-retained framework and accessible functionalized pores. This
work has enabled a general approach for introducing diverse func-
tional groups, especially large and/or reactive groups, into MOF
pores that otherwise could not be directly synthesized by conven-
tional solvothermal reactions. The tailored pore surface with the
control of both type and density of functional groups in MOFs
will extend their functionalities further toward broader applica-
tions.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ASSOCIATED CONTENT
Supporting Information
Full details for sample preparation and characterization results,
and crystallographic data (CIF). This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
zhou@mail.chem.tamu.edu
(12) As a result of small crystal size of PCN-59, X-ray diffraction data
collection only leads to a data set with the resolution of 1.8 Å.
(13) (a) Fukushima, T.; Horike, S.; Inubushi, Y.; Nakagawa, K.;
Kubota, Y.; Takata, M.; Kitagawa, S. Angew. Chem., Int. Ed. 2010, 49,
4820. (b) Wang, C.; Xie, Z.; deKrafft, K. E.; Lin, W. J. Am. Chem. Soc.
2011, 133, 13445. (c) Nagai, A.; Guo, Z.; Feng, X.; Jin, S.; Chen, X.;
Ding, X.; Jiang, D. Nat. Commun. 2011, 2:536 (1-8). (d) Nakazawa, J.;
Smith, B. J.; Stack, T. D. P. J. Am. Chem. Soc. 2012, 134, 2750. (e) Kim,
M.; Cahill, J. F.; Su, Y.; Prather, K. A.; Cohen, S. M. Chem. Sci. 2012, 3,
126.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by the U.S. Department of Energy
(DOE DE-SC0001015 and DE-AR0000073), the National Science
Foundation (NSF CBET-0930079), and the Welch Foundation
(A-1725). We are thankful to Dr. Mario Wriedt for magnetic
measurements and Prof. Daqiang Yuan for evaluating theoretical
surface area.
(14) Savonnet, M.; Canivet, J.; Gambarelli, S.; Dubois, L.; Bazer-
Bachi, D.; Lecocq, V.; Batsd, N.; Farrusseng, D. CrystEngComm 2012,
14, 4105.
(15) (a) Demessence, A.; D’Alessandro, D. M.; Foo, M. L.; Long, J. R.
J. Am. Chem. Soc. 2009, 131, 8784. (b) Zheng, B.; Bai, J.; Duan, J.;
Wojtas, L.; Zaworotko, M. J. J. Am. Chem. Soc. 2009, 133, 748. (c) An, J.;
Geib, S. J.; Rosi, N. L. J. Am. Chem. Soc. 2010, 132, 38. (d) Lin, Q.; Wu,
T.; Zheng, S.-T.; Bu, X.; Feng, P. J. Am. Chem. Soc. 2012, 134, 784. (e)
McDonald, T. M.; D’Alessandro, D. M.; Krishnac, R.; Long, J. R. Chem.
Sci. 2011, 2, 2022. (f) Li, J.-R.; Ma, Y.; McCarthy, M. C.; Sculley, J.; Yu,
J.; Jeong, H.-K.; Balbuena, P. B.; Zhou, H.-C. Coord. Chem. Rev. 2011,
255, 1791.
REFERENCES
(1) (a) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.;
Eddaoudi, M.; Kim, J. Nature 2003, 423, 705. (b) Férey, G.; Mellot-
Draznieks, C.; Serre, C.; Millange, F. Acc. Chem. Res. 2005, 38, 217. (c)
Horike, S.; Shimomura, S.; Kitagawa, S. Nat. Chem. 2009, 1, 695. (d)
Long, J. R.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1213. (e) Zhou, H.-
C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673.
(2) (a) Ma, S.; Zhou, H.-C. Chem. Commun. 2010, 46, 44. (b) Sumida,
K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z.
R.; Bae, T.-H.; Long, J. R. Chem. Rev. 2012, 112, 724. (c) Suh, M. P.;
Park, H. J.; Prasad, T. K.; Lim, D.-W. Chem. Rev. 2012, 112, 782. (d) Li,
J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869.
(3) (a) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.;
Kim, K. Nature 2000, 404, 982. (b) Ma, L.; Abney, C.; Lin, W. Chem.
Soc. Rev. 2009, 38, 1248. (c) Farrusseng, D.; Aguado, S.; Pinel, C. Angew.
Chem. Int. Ed. 2009, 48, 7502. (d) Corma, A.; García, H.; Llabrés i
Xamena, F. X. Chem. Rev. 2010, 110, 4606. (e) Jiang, H.-L.; Xu, Q.
Chem. Commun. 2011, 47, 3351.
(4) (a) Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res. 2010, 43, 1115.
(b) Jiang, H.-L.; Tatsu, Y.; Lu, Z.-H.; Xu, Q. J. Am. Chem. Soc. 2010,
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment