REVIEW SUMMARY

The Chemistry and Applications READ THE FULL ARTICLE ONLINE

http://dx.doi.org/10.1126/science.1230444

of Metal-Organic Frameworks Cite this article as H. Furukawa et al.,

Science 341, 1230444 (2013).
DOI: 10.1126/science.1230444
Hiroyasu Furukawa, Kyle E. Cordova, Michael O’Keeffe, Omar M. Yaghi*

Background: Metal-organic frameworks (MOFs) are made by linking inorganic and organic units ARTICLE OUTLINE
by strong bonds (reticular synthesis). The flexibility with which the constituents’ geometry, size, and
functionality can be varied has led to more than 20,000 different MOFs being reported and studied Design of Ultrahigh Porosity
within the past decade. The organic units are ditopic or polytopic organic carboxylates (and other Expansion of Structures by a Factor of 2 to 17
similar negatively charged molecules), which, when linked to metal-containing units, yield archi-
tecturally robust crystalline MOF structures with a typical porosity of greater than 50% of the MOF Exceptionally Large Pore Apertures
crystal volume. The surface area values of such MOFs typically range from 1000 to 10,000 m2/g, High Thermal and Chemical Stability
thus exceeding those of traditional porous materials such as zeolites and carbons. To date, MOFs
with permanent porosity are more extensive in their variety and multiplicity than any other class of Postsynthetic Modification (PSM):
porous materials. These aspects have made MOFs ideal candidates for storage of fuels (hydrogen Crystals as Molecules
and methane), capture of carbon dioxide, and catalysis applications, to mention a few. Catalytic Transformations Within the Pores

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Advances: The ability to vary the size and nature of MOF structures without changing their under- Gas Adsorption for Alternative Fuels and
lying topology gave rise to the isoreticular principle and its application in making MOFs with the Separations for Clean Air
largest pore aperture (98 Å) and lowest density (0.13 g/cm3). This has allowed for the selective
inclusion of large molecules (e.g., vitamin B12) and proteins (e.g., green fluorescent protein) and Proton Conductivity for Fuel Cell Applications
the exploitation of the pores as reaction vessels. Along these lines, the thermal and chemical stabil- MOF Nanocrystals
ity of many MOFs has made them amenable to postsynthetic covalent organic and metal-complex
The Materials Beyond
functionalization. These capabilities enable substantial enhancement of gas storage in MOFs and
have led to their extensive study in the catalysis of organic reactions, activation of small molecules
SUPPLEMENTARY MATERIALS
(hydrogen, methane, and water), gas separation, biomedical imaging, and proton, electron, and ion
conduction. At present, methods are being developed for making nanocrystals and supercrystals of Materials and Methods
MOFs for their incorporation into devices. Figs. S1 to S8
Tables S1 to S5
Outlook: The precise control over the assembly of MOFs is expected to propel this field further into
References (135–363)
new realms of synthetic chemistry in which far more sophisticated materials may be accessed. For
Related Web sites
example, materials can be envisaged as having (i) compartments linked together to operate sepa-
Cambridge Structural Database reference codes
rately, yet function synergistically; (ii) dexterity to carry out parallel operations; (iii) ability to count,
for MOFs
sort, and code information; and (iv) capability of dynamics with high fidelity. Efforts in this direction
are already being undertaken through the introduction of a large number of different functional
groups within the pores of MOFs. This yields multivariate frameworks in which the varying arrange-
ment of functionalities gives rise to materials that offer a synergistic combination of properties.
Future work will involve the assembly of chemical structures from many different types of building
unit, such that the structures’ function is dictated by the heterogeneity of the specific arrangement
of their constituents.

Metal-organic framework (MOF)

structures are amenable to expan-
sion and incorporation of multiple
functional groups within their inte-
riors. (A) The isoreticular expansion of
MOFs maintains the network’s topology
by using an expanded version of the
parent organic linker. Examples of
catalysis in MOFs are shown in the large
space created by IRMOF-74-XI; Me is a
methyl group. (B) Conceptual illustra-
tion of a multivariate MOF (MTV-MOF)
whose pores are decorated by heteroge-
neous mixtures of functionalities that
arrange in specific sequences. (Back-
ground) Optical image of zeolitic imid-
azolate framework (ZIF) crystals.

The list of author affiliations is available in the full article online.

*Corresponding author. E-mail: yaghi@berkeley.edu

974 30 AUGUST 2013 VOL 341 SCIENCE www.sciencemag.org

Published by AAAS
 REVIEW
er materials and because they lead to the previous-
ly elusive synthesis of solids by design. Unlike
other extended solids, MOFs maintain their under-
The Chemistry and Applications of lying structure and crystalline order upon expan-
sion of organic linkers and inorganic SBUs, as
Metal-Organic Frameworks well as after chemical functionalization, which
greatly widens the scope of this chemistry. We
Hiroyasu Furukawa,1,2 Kyle E. Cordova,1,2 Michael O’Keeffe,3,4 Omar M. Yaghi1,2,4* review key developments in these areas and dis-
cuss the impact of this chemistry on applications
Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates such as gas adsorption and storage, catalysis, and
strong bonds between inorganic and organic units. Careful selection of MOF constituents can proton conduction. We also discuss the concept
yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics of MTV-MOFs in relation to the sequence of func-
allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and tionality arrangement that is influenced by the
catalysis, among other applications. The precision commonly exercised in their chemical electronic and/or steric interactions among the
modification and the ability to expand their metrics without changing the underlying topology functionalities. Highly functional synthetic crys-
have not been achieved with other solids. MOFs whose chemical composition and shape of talline materials can result from the use of such
building units can be multiply varied within a particular structure already exist and may lead to techniques to create heterogeneity within MOF
materials that offer a synergistic combination of properties. structures.

he past decade has seen explosive growth of MOFs with ultrahigh porosity and unusually Design of Ultrahigh Porosity

T in the preparation, characterization, and large pore openings (5). (iii) Postsynthetic mod- During the past century, extensive work was done

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study of materials known as metal-organic ification (PSM) of MOFs—incorporating organic on crystalline extended structures in which metal
frameworks (MOFs). These materials are con- units and metal-organic complexes through re- ions are joined by organic linkers containing Lewis
structed by joining metal-containing units [sec- actions with linkers—has emerged as a powerful base–binding atoms such as nitriles and bipyridines
ondary building units (SBUs)] with organic linkers, tool for changing the reactivity of the pores (e.g., (8, 9). Although these are extended crystal struc-
using strong bonds (reticular synthesis) to create creating catalytic sites) (6). (iv) Multivariate MOFs tures and not large discrete molecules such as poly-
open crystalline frameworks with permanent po- (MTV-MOFs), in which multiple organic function- mers, they were dubbed coordination “polymers”—
rosity (1). The flexibility with which the metal alities are incorporated within a single framework, a term that is still in use today, although we prefer
SBUs and organic linkers can be varied has led have provided many opportunities for designing the more descriptive term MOFs, introduced in
to thousands of compounds being prepared and complexity within the pores of MOFs in a con- 1995 (10) and now widely accepted. Because
studied each year (Figs. 1 and 2). MOFs have ex- trolled manner (7). these structures were constructed from long or-
ceptional porosity and a wide range of potential Below, we focus on these aspects of MOF ganic linkers, they encompassed void space and
uses including gas storage, separations, and ca- chemistry because they are rarely achieved in oth- therefore were viewed to have the potential to be
talysis (2). In particular, applications in energy
technologies such as fuel cells, supercapacitors,
and catalytic conversions have made them ob-
jects of extensive study, industrial-scale produc- 7000 Total (CSD)
Extended (1D, 2D, 3D)
tion, and application (2–4). MOFs (3D)
Among the many developments made in this 12
6000
ln(No. of structures)

field, four were particularly important in advanc- 10 Doubling time

ing the chemistry of MOFs: (i) The geometric 9.3 years
principle of construction was realized by the link- 8
No. of MOF structures

5000
ing of SBUs with rigid shapes such as squares
6 5.7 years
and octahedra, rather than the simpler node-and-
spacer construction of earlier coordination net- 4000 4
works in which single atoms were linked by ditopic 3.9 years
coordinating linkers (1). The SBU approach not 2
3000
only led to the identification of a small number 0
of preferred (“default”) topologies that could be 1975 1980 1985 1990 1995 2000 2005 2010
targeted in designed syntheses, but also was cen- Year
2000
tral to the achievement of permanent porosity in
MOFs (1). (ii) As a natural outcome of the use of
SBUs, a large body of work was subsequently 1000
reported on the use of the isoreticular principle
(varying the size and nature of a structure without
changing its underlying topology) in the design 0
1972
1974
1976
1978
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
2010

1
Department of Chemistry, University of California, Berkeley,
CA 94720, USA. 2Materials Sciences Division, Lawrence Berkeley Year
National Laboratory, Berkeley, CA 94720, USA. 3Department of
Chemistry, Arizona State University, Tempe, AZ 87240, USA.
4
NanoCentury KAIST Institute and Graduate School of Energy, Fig. 1. Metal-organic framework structures (1D, 2D, and 3D) reported in the Cambridge Struc-
Environment, Water, and Sustainability (World Class Univer- tural Database (CSD) from 1971 to 2011. The trend shows a striking increase during this period for
sity), Daejeon 305-701, Republic of Korea. all structure types. In particular, the doubling time for the number of 3D MOFs (inset) is the highest
*Corresponding author. E-mail: yaghi@berkeley.edu among all reported metal-organic structures.

www.sciencemag.org SCIENCE VOL 341 30 AUGUST 2013 1230444-1

REVIEW

M2(CO2)4
Zn4O(CO2)6 M3O(CO2)6 (M = Cu, Zn, Fe, Zr6O4(OH)4- Zr6O8(CO2)8
(M = Zn, Cr, Mo, Cr, Co, and (CO2)12
In, and Ga) Ru)

M3O3(CO2)3 Al(OH)(CO2)2
(M = Zn, Mg, VO(CO2)2
Co, Ni, Mn,
Cu2(CNS)4 Zn(C3H3N2)4 Ni4(C3H3N2)8 Fe, and Cu)
In(C5HO4N2)4 Na(OH)2(SO3)3

B COOH COOH COOH COOH COOH

X OH COOH

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COOH X
O
HO HO X
OH HOOC COOH
O COOH COOH COOH COOH COOH
X H3BTE (X = C≡C)
Oxalic acid Fumaric H2BDC H2BDC-X H4DOT H2BDC-(X)2 H3BTC H3BBC (X = C6H4)
acid (X = Br, OH, (X = Me, Cl,
NO2, and NH2) COOH, OC3H5, X X
and OC7H7) HOOC COOH
HN N
COOH OH
HO3S SO3H
N NH S HOOC COOH
HOOC COOH NH2
HO OH H2N X
HOOC HOOC COOH N NH
SO3H HN N S
X X
H4ATC H3THBTS H3ImDC H3BTP DTOA H3BTB (X = CH)
H3TATB (X = N)
COOH
H HOOC COOH
N N COOH
H2N
HOOC COOH N O
COOH
N Gly-Ala OH
N N
HOOC COOH
N N N COOH
HOOC COOH HOOC
N
COOH
H4ADB TIPA ADP OH

COOH COOH
COOH COOH H6BTETCA

HOOC X X COOH
N

X Cl COOH
COOH
OH
HOOC COOH OH +
O O O O O
H6TPBTM (X = CONH) Cl
H6BTEI (X = C≡C) N N
H6BTPI (X = C6H4) N Ir
N
H6BHEI (X = C≡C−C≡C) O O O O O N
H6BTTI (X = (C6H4)2) DCDPBN
H6PTEI (X = C6H4−C≡C)
H6TTEI (X = C≡C-C6H4-C≡C) COOH
HO HO
COOH COOH COOH
H6BNETPI (X = C≡C−C6H4−C≡C−C≡C)
H6BHEHPI (X = (C6H4−C≡C)2) BPP34C10DA Ir(H2DPBPyDC)(PPy)2+ H4DH9PhDC H4DH11PhDC

Fig. 2. Inorganic secondary building units (A) and organic linkers (B) referred to in the text. Color code: black, C; red, O; green, N; yellow, S; purple,
P; light green, Cl; blue polyhedra, metal ions. Hydrogen atoms are omitted for clarity. AIPA, tris(4-(1H-imidazol-1-yl)phenyl)amine; ADP, adipic acid; TTFTB4–,
4,4′,4′′,4′′′-([2,2′-bis(1,3-dithiolylidene)]-4,4′,5,5′-tetrayl)tetrabenzoate.

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permanently porous, as is the case for zeolites. The gas identified the adsorption sites within the pores Another MOF of interest is known as HKUST-1
porosity of these compounds was investigated in (18). The zinc oxide SBU, the faces, and, sur- [Cu3(BTC)2; BTC3– = benzene-1,3,5-tricarboxylate]
the 1990s by forcing gas molecules into the crev- prisingly, the edges of the BDC2– linker serve as (35); it is composed of Cu paddlewheel [Cu2(CO2)4]
ices at high pressure (11). However, proof of per- adsorption sites. This study uncovered the origin SBUs (Fig. 2A) and a tritopic organic linker, BTC3–.
manent porosity requires measurement of reversible of the high porosity and has enabled the design of Several isoreticular structures have been made
gas sorption isotherms at low pressures and tem- MOFs with even higher porosities (Fig. 4 and ta- by expansion with TATB3– [4,4′,4′′-(1,3,5-triazine-
peratures. Nonetheless, as we remarked at that ble S3). Moreover, it has been reported that ex- 2,4,6-triyl)tribenzoate], TATAB3– [4,4′,4′′-((1,3,5-
time (12), it was then commonplace to refer to panded tritopic linkers based on alkyne rather than triazine-2,4,6-triyl)tris(azanediyl))tribenzoate],
materials as “porous” and “open framework” even phenylene units should increase the number of TTCA3– [triphenylene-2,6,10-tricarboxylate],
though such proof was lacking. The first proof of adsorption sites and increase the surface area (19). HTB3– [4,4′,4′′-(1,3,3a1,4,6,7,9-heptaazaphenalene-
permanent porosity of MOFs was obtained by mea- NU-110 [Cu3(BHEHPI); BHEHPI6– = 5,5′,5′′- 2,5,8-triyl)tribenzoate], and BBC3– linkers (tbo
surement of nitrogen and carbon dioxide isotherms ((((benzene-1,3,5-triyltris(benzene-4,1-diyl)) net; Fig. 3B, fig. S1 and S5, and tables S1 and
on layered zinc terephthalate MOF (12). tris(ethyne-2,1-diyl))-tris(benzene-4,1-diyl)) S2) (21, 36–39). The cell volume for the largest
A major advance in the chemistry of MOFs tris(ethyne-2,1-diyl))triisophthalate], whose organic reported member [MOF-399, Cu3(BBC)2] is
came in 1999 when the synthesis, x-ray single- linker is replete with such edges, displayed a sur- 17.4 times that of HKUST-1. MOF-399 has the
crystal structure determination, and low-temperature, face area of 7140 m2/g (Table 1) (7, 17, 20–32). highest void fraction (94%) and lowest density
low-pressure gas sorption properties were reported For many practical purposes, such as storing (0.126 g/cm3) of any MOF reported to date (21).
for the first robust and highly porous MOF, MOF-5 gases, calculating the surface area per volume Cu paddlewheel units are also combined with
(13). This archetype solid comprises Zn4O(CO2)6 is more relevant. By this standard, the value for various lengths of hexatopic linkers to form an-
octahedral SBUs each linked by six chelating MOF-5, 2200 m2/cm3, is among the very best other isoreticular series. The first example of one
1,4-benzenedicarboxylate (BDC2–) units to give reported for MOFs (for comparison, the value for of these MOFs is Zn3(TPBTM) [TPBTM6– =
a cubic framework (Fig. 2, figs. S2 and S3, and NU-110 is 1600 m2/cm3). Note that the external 5,5′,5′′-((benzene-1,3,5-tricarbonyl)tris(azanediyl))

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tables S1 and S2). The architectural robustness of surface area of a nanocube with edges measuring triisophthalate], which has a ntt net (40). Shortly
MOF-5 allowed for gas sorption measurements, 3 nm would be 2000 m2/cm3. However, nano- after this report, several isoreticular MOF struc-
which revealed 61% porosity and a Brunauer- crystallites on this scale with “clean” surfaces tures were synthesized (Fig. 3C and fig. S6)
Emmett-Teller (BET) surface area of 2320 m2/g would immediately aggregate, ultimately leaving (19, 20, 24, 41–48): Cu3(TPBTM), Cu3(TDPAT),
(2900 m2/g Langmuir). These values are substan- their potential high surface area inaccessible. NOTT-112 [Cu3(BTPI)], NOTT-116 [also known
tially higher than those commonly found for zeo- as PCN-68; Cu3(PTEI)], PCN-61 [Cu3(BTEI)],
lites and activated carbon (14). Expansion of Structures by a Factor of 2 to 17 PCN-66 [Cu3(NTEI)], PCN-69 [also known as
To prepare MOFs with even higher surface A family of 16 cubic MOFs—IRMOF-1 [also NOTT-119; Cu3(BTTI)], PCN-610 [also known
area (ultrahigh porosity) requires an increase in known as MOF-5, which is the parent MOF of as NU-100; Cu3(TTEI)], NU-108 [Cu3(BTETCA)],
storage space per weight of the material. Longer the isoreticular (IR) series] to IRMOF-16—with NU-109 [Cu3(BNETPI)], NU-110, and NU-111
organic linkers provide larger storage space and a the same underlying topology (isoreticular) was [Cu3(BHEI)] TDPAT6– = 5,5′,5′′-((1,3,5-triazine-
greater number of adsorption sites within a given made with expanded and variously functionalized 2,4,6-triyl)tris(azanediyl))triisophthalate; BTPI6– =
material. However, the large space within the crys- organic linkers (figs. S2 and S3) (1, 5). This de- 5,5′,5′′-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))
tal framework makes it prone to form interpen- velopment heralded the potential for expanding triisophthalate; PTEI6– = 5,5′,5′′-((benzene-1,3,5-
etrating structures (two or more frameworks grow and functionalizing MOFs for applications in gas triyl-tris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))
and mutually intertwine together). The most effec- storage and separations. The same work demon- triisophthalate; BTEI6– = 5,5′,5′′-(benzene-1,3,5-
tive way to prevent interpenetration is by making strated that a large number of topologically iden- triyl-tris(ethyne-2,1-diyl))triisophthalate; NTEI6– =
MOFs whose topology inhibits interpenetration tical but functionally distinctive structures can be 5,5′,5′′-((nitrilotris(benzene-4,1-diyl))tris(ethyne-
because it would require the second framework made. Note that the topology of these isoreticular 2,1-diyl))triisophthalate; BTTI6– = 5,5′,5′′-
to have a different topology (15). Additionally, MOFs is typically represented with a three-letter (benzene-1,3,5-triyl-tris(biphenyl-4,4′-diyl))
it is important to keep the pore diameter in the code, pcu, which refers to its primitive cubic net triisophthalate; TTEI6– = 5,5′,5′′-(((benzene-
micropore range (below 2 nm) by judicious se- (33). One of the smallest isoreticular structures 1,3,5-triyl-tris(ethyne-2,1-diyl))tris(benzene-4,1-
lection of organic linkers in order to maximize of MOF-5 is Zn4O(fumarate)3 (34); one of the diyl))tris(ethyne-2,1-diyl))triisophthalate;
the BET surface area of the framework, because it largest is IRMOF-16 [Zn4O(TPDC)3; TPDC2– = BTETCA6– = 5′,5′′′′,5′′′′′′′-(benzene-1,3,5-triyl-tris
is known that BET surface areas obtained from terphenyl-4,4′′-dicarboxylate] (5) (fig. S2). In this (ethyne-2,1-diyl))tris(([1,1′:3′,1′′-terphenyl]-4,4′′-
isotherms are similar to the geometric surface areas expansion, the unit cell edge is doubled and its dicarboxylate)); BNETPI6– = 5,5′,5″-(((benzene-
derived from the crystal structure (16). In 2004, volume is increased by a factor of 8. The degree 1,3,5-triyl-tris(ethyne-2,1-diyl))tris(benzene-4,1-diyl))
MOF-177 [Zn4O(BTB)2; BTB = 4,4′,4′′-benzene- of interpenetration, and thus the porosity and den- tris(buta-1,3-diyne-4,1-diyl))triisophthalate;
1,3,5-triyl-tribenzoate] was reported with the high- sity of these materials, can be controlled by chang- BHEI6– = 5,5′,5″-(benzene-1,3,5-triyl-tris(buta-
est surface area at that time (BET surface area = ing the concentration of reactants, temperature, or 1,3-diyne-4,1-diyl))triisophthalate]. Isoreticular
3780 m2/g, porosity = 83%; Figs. 3A and 4) (15), other experimental conditions (5). materials are not necessarily expansions of the
which satisfies the above requirements. In 2010, The concept of the isoreticular expansion is original parent MOF, as exemplified by NU-108,
the surface area was doubled by MOF-200 and not simply limited to cubic (pcu) structures, as because the ntt family has a linker (BTETCA6–)
MOF-210 [Zn4O(BBC)2 and (Zn4O)3(BTE)4(BPDC)3, illustrated by the expansion of MOF-177 to give with two branching points and two kinds of links
respectively; BBC3– = 4,4′,4′′-(benzene-1,3,5- MOF-180 [Zn4O(BTE)2] and MOF-200, which (figs. S1B and S7).
triyl-tris(benzene-4,1-diyl))tribenzoate; BTE = use larger triangular organic linkers (qom net; Fig. A wide variety of metal ions form metal-
4,4′,4′′-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)) 3A and fig. S4) (15, 17). Contrary to the MOF-5 carboxylate units, and isostructural MOFs can be
tribenzoate; BPDC = biphenyl-4,4′-dicarboxylate] type of expanded framework, expanded structures synthesized by replacing the metal ions in the
to produce ultrahigh surface areas (4530 m2/g of MOF-177 are noninterpenetrating despite the inorganic SBUs. Indeed, after the appearance of
and 6240 m2/g, respectively) and porosities (90% high porosity of these MOFs (89% and 90% for HKUST-1 [Cu3(BTC)2], an isostructural series of
and 89%) (17). MOF-180 and MOF-200, respectively). These HKUST-1 [M3(BTC)2, where M = Zn(II), Fe(II),
An x-ray diffraction study performed on a sin- results highlight the critical role of selecting Mo(II), Cr(II), Ru(II)] was prepared by sever-
gle crystal of MOF-5 dosed with nitrogen or argon topology. al groups (fig. S5) (49–53). In the same way as

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REVIEW

A Tritopic linker B Tritopic linker

Zn4O(CO2)6 Cu2(CO2)4

× 5.5

× 1.8 Cu3(BTC)2, HKUST-1

MOF-199 (tbo) Cu3(TATB)2, PCN-6’ (tbo)
Zn4O(BTE)2
Zn4O(BTB)2 MOF-180 (qom) × 17.4
MOF-177 (qom)

× 2.7

Downloaded from http://science.sciencemag.org/ on July 18, 2018

20 Å Zn4O(BBC)2
20 Å
MOF-200 (qom) Cu3(BBC)2,
MOF-399 (tbo)

Hexatopic linker
C D

Cu2(CO2)4
× 6.5

Mg3O3(CO2)3

Mg2(DOT), Mg-MOF-74
(IRMOF-74-I) (etb)
Mg2(DH5PhDC),
IRMOF-74-V (etb)
Tetratopic × 16.1
linker
Cu3(TDPAT) (ntt) × 2.2

Cu3(NTEI),
× 6.0 PCN-66 (ntt)

30 Å
Cu3(BHEHPI),
Mg2(DH11PhDC),
NU-110 (ntt) 30 Å IRMOF-74-XI (etb)

Fig. 3. Isoreticular expansion of metal-organic frameworks with comparison of the smallest, medium, and largest crystalline structures of
qom, tbo, ntt, and etb nets. (A to D) The isoreticular (maintaining same MOFs representative of these nets. The large yellow and green spheres
topology) expansion of archetypical metal-organic frameworks resulting represent the largest sphere that would occupy the cavity. Numbers above
from discrete [(A), (B), and (C)] and rod inorganic SBUs (D) combined with each arrow represent the degree of volume expansion from the smallest
tri-, hexa-, and tetratopic organic linkers to obtain MOFs in qom (A), tbo framework. Color code is same as in Fig. 2; hydrogen atoms are omitted for
(B), ntt (C), and etb (D) nets, respectively. Each panel shows a scaled clarity.

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discrete inorganic SBUs, the infinite inorganic but rarely are they of appropriate size to permit 4, 5, 6, 7, 9, and 11 phenylene units [DH2PhDC4–
rod-type SBUs were also used to synthesize inclusion of large molecules such as proteins. to DH11PhDC4–, respectively; Fig. 2B, Fig. 3D, and
isostructural MOF-74 [Zn2(DOT); DOT = The best way to increase pore apertures is to use figs. S1B and S8] (22). Crystal structures revealed
dioxidoterephthalate] (54) using divalent metal infinite rod-shaped SBUs with linkers of arbitrary that pore apertures for this series of MOF-74 struc-
ions such as Mg, Co, Ni, and Mn (fig. S8) (55). length providing periodicity in the other two di- tures (termed IRMOF-74-I to IRMOF-74-XI) ranged
mensions, which does not allow for interpene- from 14 to 98 Å. The presence of the large pore
Exceptionally Large Pore Apertures trating structures. This strategy was implemented apertures was also confirmed by transmission elec-
Pore openings of MOFs are typically large enough by expanding the original phenylene unit of MOF-74 tron microscopy (TEM) and scanning electron
(up to 2 nm) to accommodate small molecules, [M2(DOT); M2+ = Zn, Mg] structure (54) to 2, 3, microscopy (SEM) observation as well as argon
adsorption measurements of the guest-free mate-
rials. As expected, the pore aperture of IRMOF-74-
IX is of sufficient size to allow for green fluorescent
8000
NU-110 protein (barrel structure with diameter of 34 Å
Typical NOTT-119 (2.35)
MOFs (4.40) and length of 45 Å) to pass into the pores without
7000 conventional MOF-210 (3.60) unfolding. More important, the large pore aperture
porous
NU-100 (2.82) is of benefit to the surface modification of the pores
materials
6000
with various functionalities without sacrificing the
MOF-177 (2.00)
porosity (22). An oligoethylene glycol–functionalized
BET surface area (m2/g)

IRMOF-20 (1.53) UMCM-2

MOF-5 (1.48) (2.32) DUT-49 IRMOF-74-VII [Mg2(DH7PhDC-oeg)] allows in-
5000 (2.91) clusion of myoglobin, whereas IRMOF-74-VII
MIL-101
with hydrophobic hexyl chains showed a negli-
MIL-101 (2.00) MOF-5 (2.15)
gible amount of inclusion.

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4000 MOF-177 (1.59)
(1.56)

MOF-5 (1.20) High Thermal and Chemical Stability

Carbons (0.60)

3000 Because MOFs are composed entirely of strong

MOF-5

Bio-MOF-100 (4.30)
bonds (e.g., C-C, C-H, C-O, and M-O), they show
Zeolites (0.30)

(1.04)
Silicas (1.15)

DUT-23(Co) (2.03)
NOTT-112 (1.59)

MOF-200 (3.59) high thermal stability ranging from 250° to 500°C

UMCM-1 (2.24)

2000
(5, 56–58). It has been a challenge to make chem-
PCN-6 (1.41)
MIL-100 (1.10)

ically stable MOFs because of their susceptibility

1000 to link-displacement reactions when treated with
solvents over extended periods of time (days). The
0 first example of a MOF with exceptional chemical
1999 2004 2006 2008 2010 2012 stability is zeolitic imidazolate framework–8 [ZIF-
Year 8, Zn(MIm)2; MIm– = 2-methylimidazolate], which
was reported in 2006 (56). ZIF-8 is unaltered after
Fig. 4. Progress in the synthesis of ultrahigh-porosity MOFs. BET surface areas of MOFs and typical immersion in boiling methanol, benzene, and water
conventional materials were estimated from gas adsorption measurements. The values in parentheses for up to 7 days, and in concentrated sodium
represent the pore volume (cm3/g) of these materials. hydroxide at 100°C for 24 hours.

Table 1. Typical properties and applications of metal-organic frameworks. Metal-organic frameworks exhibiting the lowest and highest values
for the indicated property, and those reported first for selected applications, are shown.

Property or application Compound Achieved value or year of report Reference

Lowest reported value
Density MOF-399 0.126 g/cm3 (21)
Highest reported value
Pore aperture IRMOF-74-XI 98 Å (22)
Number of organic linkers MTV-MOF-5 8 (7)
Degrees of interpenetration Ag6(OH)2(H2O)4(TIPA)5 54 (23)
BET surface area NU-110 7140 m2/g (20)
Pore volume NU-110 4.40 cm3/g (20)
Excess hydrogen uptake (77 K, 56 bar) NU-100 9.0 wt% (24)
Excess methane uptake (290 K, 35 bar) PCN-14 212 mg/g (25)
Excess carbon dioxide uptake (298 K, 50 bar) MOF-200 2347 mg/g (17)
Proton conductivity (98% relative humidity, 25°C) (NH4)2(ADP)[Zn2(oxalate)3]·3H2O 8 × 10−3 S/cm (26)
Charge mobility Zn2(TTFTB) 0.2 cm2/V·s (27)
Lithium storage capacity (after 60 cycles) Zn3(HCOO)6 560 mAh/g (28)
Earliest report
Catalysis by a MOF Cd(BPy)2(NO3)2 1994 (29)
Gas adsorption isotherm and permanent porosity MOF-2 1998 (12)
Asymmetric catalysis with a homochiral MOF POST-1 2000 (31)
Production of open metal site MOF-11 2000 (30)
PSM on the organic linker POST-1 2000 (31)
Use of a MOF for magnetic resonance imaging MOF-73 2008 (32)

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REVIEW
MOFs based on the Zr(IV) cuboctahedral SBU [CdCl2(DCDPBN)], used orthogonal dihydroxy leaching out of the MOF. The porphyrin metal sites
(Fig. 2A) also show high chemical stability; functionalities to coordinate titanium isopropoxide were subsequently metallated and used for the
UiO-66 [Zr6O4(OH)4(BDC)6] and its NO2- and [Ti(OiPr)4], thus yielding a highly active, enantio- oxidation of cyclohexane. The same approach has
Br-functionalized derivatives demonstrated high selective asymmetric Lewis acid catalyst (67). been applied to several other systems in which
acid (HCl, pH = 1) and base resistance (NaOH, UMCM-1-NH2 was also functionalized in such a polyoxometalates are encapsulated within MIL-
pH = 14) (57, 58). The stability also remains manner to incorporate salicylate chelating groups, 101(Cr) and HKUST-1 for applications in the
when tetratopic organic linkers are used; both which were subsequently metallated with Fe(III) oxidation of alkenes and the hydrolysis of esters
MOF-525 [Zr6O4(OH)4(TpCPP-H2)3; TpCPP = and used as a catalyst for Mukaiyama aldol reac- in excess water (79, 80).
tetra-para-carboxyphenylporphyrin] and 545 tions over multiple catalytic cycles without loss of Integration of nanoparticles for catalysis by
[Zr6O8(TpCPP-H2)2] are chemically stable in activity or crystallinity (68). Indeed, the remarkable PSM has been carried out to enhance particle
methanol, water, and acidic conditions for 12 hours retention of MOF crystallinity and porosity after stability or to produce uniform size distributions.
(59). Furthermore, a pyrazolate-bridged MOF undergoing the transformation reactions clearly dem- Palladium nanoparticles were incorporated with-
[Ni3(BTP)2; BTP3– = 4,4′,4″-(benzene-1,3,5- onstrates the use of MOF crystals as molecules (69). in MIL-101(Cr) for cross-coupling reactions
triyl)tris(pyrazol-1-ide)] is stable for 2 weeks in a (81, 82). Most recently, a bifunctional catalytic
wide range of aqueous solutions (pH = 2 to 14) at Catalytic Transformations Within the Pores MOF {Zr6O4(OH)4[Ir(DPBPyDC)(PPy)2·X]6;
100°C (60). The high chemical stability observed The high surface areas, tunable pore metrics, and DPBPyDC2– = 4,4′-([2,2′-bipyridine]-5,5′-
in these MOFs is expected to enhance their per- high density of active sites within the very open diyl)dibenzoate, PPy = 2-phenylpyridine} capable
formance in the capture of carbon dioxide from structures of MOFs offer many advantages to of water-splitting reactions was reported (83). This
humid flue gas and extend MOFs’ applications to their use in catalysis (table S5). MOFs can be MOF uses the organic linker and an encapsulated
water-containing processes. used to support homogeneous catalysts, stabi- nanoparticle to transfer an electron to a proton in
lize short-lived catalysts, perform size selectiv- solution, leading to hydrogen evolution.
Postsynthetic Modification (PSM): ity, and encapsulate catalysts within their pores

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Crystals as Molecules (70). The first example of catalysis in an ex- Gas Adsorption for Alternative Fuels and
The first very simple, but far from trivial, example tended framework, reported in 1994, involved the Separations for Clean Air
of PSM was with the Cu paddlewheel carboxylate cyanosilylation of aldehydes in a Cd-based frame- Much attention is being paid to increasing the
MOF-11 [Cu2(ATC); ATC4– = adamantane-1,3,5,7- work [Cd(BPy)2(NO3)2; BPy = 4,4′-bipyridine] storage of fuel gases such as hydrogen and meth-
tetracarboxylate] (30). As-prepared Cu atoms are as a result of axial ligand removal (29). This ane under practical conditions. The first study of
bonded to four carboxylate O atoms, and the co- study also highlighted the benefits of MOFs as hydrogen adsorption was reported in 2003 for
ordination shell is completed typically with coor- size-selective catalysts by excluding large sub- MOF-5 (84). This study confirmed the potential
dinated water (Fig. 2A). Subsequent removal of strates from the pores. of MOFs for application to hydrogen adsorption,
the water from the immobilized Cu atom leaves a In 2006, it was shown that removal of solvent which has led to the reporting of hydrogen ad-
coordinatively unsaturated site (“open metal site”). from HKUST-1 exposes open metal sites that sorption data for hundreds of MOFs (85). In gen-
Many other MOFs with such sites have now been may act as Lewis acid catalysts (71). MIL-101 eral, the functionality of organic linkers has little
generated and have proved to be exceptionally [Cr3X(H2O)2O(BDC)3; X = F, OH] and Mn-BTT influence on hydrogen adsorption (86), whereas
favorable for selective gas uptake and catalysis {Mn3[(Mn4Cl)3(BTT)8]2; BTT3– = 5,5′,5″-(benzene- increasing the pore volume and surface area of
(61–63). 1,3,5-triyl)tris(tetrazol-2-ide)} have also been iden- MOFs markedly enhances the gravimetric hydro-
The first demonstration of PSM on the or- tified as Lewis acid catalysts in which the metal gen uptake at 77 K and high pressure, as exem-
ganic link of a MOF was reported in 2000 for a oxide unit functions as the catalytic site upon lig- plified by the low-density materials: NU-100 and
homochiral MOF, POST-1 [Zn3(m3-O)(D-PTT)6; and removal (62, 72). In addition, alkane oxida- MOF-210 exhibit hydrogen adsorption as high as
D-PTT – = (4S,5S )-2,2-dimethyl-5-(pyridin-4- tion, alkene oxidation, and oxidative coupling 7.9 to 9.0 weight percent (wt%) at 56 bar for both
ylcarbamoyl)-1,3-dioxolane-4-carboxylate] (31). reactions have also been reported; they all rely on MOFs and 15 wt% at 80 bar for MOF-210 (17, 24).
It involved N-alkylation of dangling pyridyl func- the metal sites within the SBUs for catalytic ac- However, increasing the surface area is not always
tionalities with iodomethane and 1-iodohexane to tivity (73–75). The study of methane oxidation an effective tool for increasing the volumetric
produce N-alkylated pyridinium ions exposed to in vanadium-based MOF-48 {VO[BDC-(Me)2]; hydrogen adsorption, which can be accomplished
the pore cavity. Me = methyl} is promising because the catalytic by increasing the adsorption enthalpy of hy-
More recently, PSM was applied to the dan- turnover and yield for this oxidation far exceed drogen (Qst) (87). In this context, open metal sites
gling amine group of IRMOF-3 [Zn4O(BDC-NH2)3] those of the analogous homogeneous catalysts (73). have been suggested and used to enhance the
crystals (6). The MOF was submerged in a One early example of the use of a MOF as a het- hydrogen uptake capacity and to improve Qst
dichloromethane solution containing acetic anhy- erogeneous catalyst is PIZA-3 [Mn2(TpCPP)2Mn3], (61, 85). Two MOFs with this characteristic,
dride to give the amide derivative in >80% yield. which contains a metalloporphyrin as part of Zn3(BDC)3[Cu(Pyen)] [Pyen2– =5,5′-((1E,1′E)-(ethane-
Since then, a large library of organic reactions the framework (76). PIZA-3 is capable of hydrox- 1,2-diyl-bis(azanylylidene))bis(methanylylidene))bis(3-
have been used to covalently functionalize MOF ylating alkanes and catalyzes the epoxidation of methylpyridin-4-ol)] and Ni-MOF-74, have the
backbones (table S4) (64, 65). olefins. Schiff-base and binaphthyl metal complexes highest reported initial Qst values: 15.1 kJ/mol and
UMCM-1-NH2 [(Zn4O)3(BDC-NH2)3(BTB)4] have also been incorporated into MOFs to achieve 12.9 kJ/mol, respectively (58, 88). Metal impreg-
was also acylated with benzoic anhydride to olefin epoxidation and diethyl zinc (ZnEt2) addi- nation has also been suggested by computation
produce the corresponding amide functionality tions to aromatic aldehydes, respectively (67, 77). as a method for increasing the Qst values (89).
within the pores (66). The structures of both The incorporation of porphyrin units within Experiments along these lines show that dop-
IRMOF-3 and UMCM-1-NH2 after modification the pores of MOFs can be accomplished during ing MOFs with alkali metal cations yields only
showed increased hydrogen uptake relative to the the synthesis (a “ship-in-a-bottle” approach that cap- modest enhancements in the total hydrogen up-
parent MOFs, even though there was a reduction tures the units as the pores form), as illustrated for take and Qst values (90, 91). Although some chal-
in overall surface area (66). PSM has also been the zeolite-like MOF rho-ZMOF [In(HImDC)2·X; lenges remain in meeting the U.S. Department
used to dangle catalytically active centers within HImDC2– = imidazoledicarboxylate, X– = coun- of Energy (DOE) system targets (5.5 wt% and
the pores. In an example reported in 2005, a Cd-based teranion] (78). The pores of this framework accom- 40 g/liter at –40° to 60°C below 100 bar) for hy-
MOF built from 6,6′-dichloro-4,4′-di(pyridin-4-yl)- modate high porphyrin loadings, and the pore drogen adsorption (85), Mercedes-Benz has al-
[1,1′-binaphthalene]-2,2′-diol (DCDPBN), aperture is small enough to prevent porphyrin from ready deployed MOF hydrogen fuel tanks in a

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 REVIEW
fuel cell–powered demonstration model, the gases requires high selectivity in the presence of 1,2,4,5-tetrakisphosphonomethylbenzene] (107).
F125 (92). water, it is useful to target MOFs in which the Alternatively, high proton conductivity is also ob-
An alternative high-density fuel source to hy- competition between carbon dioxide and water served in one-dimensional (1D) metal-organic
drogen and gasoline is natural gas (methane). The for adsorption is minimized. In this respect, chem- structures lacking any acidic functionality, as in
first study of high-pressure methane adsorption ical binding of carbon dioxide in a recent MOF to Fe(oxalate)(H2O)2. Here, coordinated water mol-
in an extended metal-organic structure was re- make organic carbonates reversibly is a promising ecules act as proton donors, with their 1D arrange-
ported in 2000 for CuSiF6(BPy)2 (93), which dem- approach (99). ment within crystals facilitating the rate of proton
onstrated an uptake capacity of 104 mg/g at 36 atm Gas storage experiments on MOFs have also transport (108).
and 298 K. As is the case for hydrogen adsorption, been extended to the separation of hydrocarbons, If MOFs are to serve as proton conductors for
the total gravimetric methane uptake capacity is toxic molecules (e.g., ammonia and chlorine), and practical applications, they must be able to func-
generally proportional to the pore volume of MOFs. water. For instance, Cu2(PZDC)2(Pyz) (PZDC = tion at relatively high operating temperatures (120°
The calculated total uptake values for MOF-177, pyrazine-2,3-dicarboxylate; Pyz = pyrazine) se- to 180°C) and in anhydrous conditions (109). A
MOF-200, and MOF-210 are 345 mg/g, 446 mg/g, lectively takes up acetylene over carbon dioxide simple strategy that may be used to meet these
and 476 mg/g, respectively, at 80 bar and 298 K. through hydrogen bonding between acetylene and practical considerations is the impregnation of MOFs
These values are much greater than those of any oxygen atoms on the MOF internal surface (100). with amphoteric molecules such as imidazole.
other MOF (17). The amount of methane stored Ammonia was previously considered to be too reac- For instance, 1H-1,2,4-triazole–loaded PCMOF-2
in a vessel filled with one of these MOFs is at tive for MOFs; however, chemically stable Zr-MOFs, [Na3(THBTS); THBTS3– = 2,4,6-trihydroxy-1,3,5-
least double the amount that could be stored in an such as UiO-66-NH2 [Zr6O4(OH)4(BDC-NH2)6] benzenetrisulfonate] has a higher conductivity than
empty vessel at room temperature and pressures and other derivatives, maintain their structures af- the MOF without triazole (110). Similar results were
up to 80 bar (17). This technology is now being ter the process of ammonia adsorption and de- also obtained for imidazole-doped Al(OH)(NDC)
commercialized by BASF for automobile fueling sorption (101). (NDC = 1,4-naphthalenedicarboxylate) (111). Even
(94). The optimal material is not necessarily the Gas separation processes in MOFs generally higher conductivity was observed when histamine

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one with highest uptake, but rather one that al- rely on both the size of the pores and the affinity was used as a proton carrier (112). These exciting
lows minimal uptake at low pressure and highest of MOFs for the targeted gases. After the dis- results indicate that high-mobility proton carriers
uptake at higher pressure so as to maximize the covery of permanent porosity of MOFs, equilib- situated within the pore play a key role in achiev-
working capacity. rium adsorption isotherms for various gases were ing MOFs with high proton conductivity.
MOFs also offer reversible carbon dioxide collected to estimate potential gas selectivity. High Extensive research has been devoted to re-
adsorption and are promising materials for the selectivity calculated from equilibrium data does alizing polymer-supported electrolyte membrane
selective capture of carbon from the atmosphere not guarantee high selectivity under dynamic gas fuel cells consisting of perfluorosulfonic acid
and flue gas. Carbon dioxide adsorption in MOFs separation conditions. The latter is desirable in in- polymers (e.g., Nafion); however, these polymers
was first reported in 1998 for MOF-2 [Zn(BDC)] dustrial processes, because the diffusion rate and have some drawbacks, such as operation temper-
(12). In 2005, a detailed study of carbon dioxide Qst value of gas binding in the adsorbent are sen- ature, humidity, and cost (109). MOFs will be
adsorption in a series of MOFs at room temper- sitive to the operating conditions. One of the ear- attractive candidates for this application because
ature showed MOF-177 to have an uptake ca- liest examples of a dynamic separation was performed of their tunable pore size and functionality as well
pacity of 1470 mg/g at 35 bar (95). This uptake of using a gas chromatographic column filled with as their chemical and thermal stability.
carbon dioxide exceeded that of any known po- MOF-508 [Zn2(BDC)2(BPy)] to separate alkanes
rous material under such conditions. The large such as n-pentane, n-hexane, 2,2-dimethylbutane, MOF Nanocrystals
quadrupole moment of carbon dioxide molecules and 2-methylpentane (102). Another early exam- The advantages of MOFs are not solely limited to
causes them to interact with the framework more ple is the removal of tetrahydrothiophene (THT) properties that originate from their pore structure
strongly than hydrogen and methane. As expected, from methane by means of a fixed bed containing and functionalities. By virtue of the diverse syn-
the best excess carbon dioxide uptake reported Cu3(BTC)2 (3). The color of the Cu3(BTC)2 thetic procedures reported, the size and morphol-
to date was observed in a MOF with ultrahigh changed from deep blue to light green, indicating ogy of MOF nanocrystals can be precisely controlled
porosity, MOF-200 (2437 mg/g at 50 bar and that THT was adsorbed to the copper open metal (113). Several groups have recently reviewed the
298 K) (17). In practical terms, a gas tank filled sites. More recently, it has been reported that Mg preparation of MOF nanocrystals for membrane
with MOF-177 or MOF-200 would store 9 times and Fe-MOF-74, packed in a column, exhibit en- and thin-film applications (2, 114, 115).
or 17 times as much carbon dioxide at 35 bar, hanced carbon dioxide separation from methane In 2003, the synthesis of nanocrystalline MOFs
respectively, as the corresponding pressurized tank and C1 to C3 hydrocarbon, respectively (61, 103). was accomplished at room temperature for
without MOF. On the other hand, many carbon MOF-5, affording crystal sizes of 70 to 90 nm
dioxide capture applications will operate at low Proton Conductivity for Fuel Cell Applications (116). The obtained MOF samples were crystal-
pressure so that the Henry’s law constant (i.e., The use of MOFs as inexpensive proton-conducting line and porous but without controlled morphol-
initial slope of the isotherm) can be used as an membranes for fuel cell applications represents a ogy. It was not until 2009 that precise control of
indicator of the carbon dioxide selectivity. MOFs new direction in MOF research (104). The first MOF nanocrystal morphology was reported (117):
with open metal sites were found to have de- conductivity measurements were performed on rhombic dodecahedral ZIF-8 nanocrystals with
sirable high initial Qst values of 62 kJ/mol and Cu(DTOA)(HOC2H4)2, albeit with a relatively low an estimated average diameter of 40 nm, narrow
47 kJ/mol for MIL-101(Cr) and Mg-MOF-74, reported conductivity (105). It is now understood size distribution, high crystallinity, porosity, and
respectively (96, 97), thereby offering enhanced that any improvement in the water-mediated proton chemical stability. A follow-up study revealed that
carbon dioxide uptake and selectivity at low pres- conductivity of MOFs requires the addition of an the nucleation process in ZIF nanocrystal forma-
sures. Basic nitrogen centers have also been post- acid functionality, such as carboxylic, phosphonic, tion is initially slow, followed by a rapid process
synthetically added to MOFs with open metal sites or sulfonic acid, as demonstrated by several func- of crystal growth (118). Interestingly, the study
by using N,N′-dimethylethylenediamine (mmen), tionalized versions of MIL-53 [Fe(OH)(BDC-X); showed that the morphology of the nanocrystals
where the highest initial Qst for H3[(Cu4Cl)3 X = H, NH2, OH, (COOH)2] (106). This finding is transformed from cubic to rhombic dodecahe-
(BTTri)8(mmen)12] [BTTri3– = 4,4′,4″-(benzene- further supported by the demonstrated high proton dra in the last stage of crystal formation. This
1,3,5-triyl)tris(1,2,3-triazol-1-ide)] is estimated to conductivity—2.5 × 10−3 S/cm at 98% relative result indicated that the morphology of nano-
be 96 kJ/mol (98). Because the ideal material for humidity and 60°C—of MOFs with highly acidic crystals can be tuned through the optimization
carbon dioxide capture from flue and combustion pores [PCMOF-5, La(H5DTP)(H2O)3; DTP8– = of synthetic conditions. Furthermore, soc-MOF-1

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REVIEW
{[M6O2(ADB)3(H2O)6](H2O)6(NO3)2; ADB4– = call this space “the materials beyond.” One can comprising a single organic linker (7). This find-
3,3′,5,5′-azobenzenetetracarboxylate; M = In(III), imagine materials with unique sequences of build- ing clearly demonstrates that MTV-MOFs are not
Ga(III)} and HKUST-1 nanocrystals have adopted ing units that code for specific functions. Materials simple linear combinations of their constituents.
several morphologies with their respective di- capable of complex operations and transforma- Precise control of the functionality arrangement
ameters in the submicrometer to micrometer tions could be used in applications such as con- in MOFs is still a looming challenge; however, a
range (119, 120). version of carbon dioxide to fuels, methane to new strategy that is widely used for peptide syn-
The assembly of MOF nanocrystals is of par- higher alkanes, and water to hydrogen. Once we thesis has been used to systematically control a se-
ticular interest in MOF research because orga- begin to think in terms of heterogeneity of com- quence of functionalities via solid-phase synthesis.
nized nanostructures comprising one or more position, shape, size, and orientation of building Metal-organic complex arrays (MOCAs) are het-
nanocrystal types may have distinctive properties units, there is no limit to the different scenarios erometallic complexes in which different metal-
similar to those seen in metal nanocrystal super- for making materials endowed with unusual com- organic centers are connected to an amino acid
lattices (121). Only a limited number of examples plexity. Such materials go beyond merely linking backbone (Fig. 6B) (127). The solid-phase syn-
have been reported to date; however, closely packed building units through strong bonds, as in MOFs. thesis strategy for connecting these units allowed
2D superlattice structures of ZIF-8, soc-MOF-1, In 2010, a simple strategy was proposed and for careful control of the sequence, nuclearity, and
and UiO-66 were observed by SEM (119, 122, 123). demonstrated to introduce further complexity to length of up to six metal centers including Pt(II),
Applying an ac electric field created linear chain crystalline structures (Fig. 6A) (7). In this work, Rh(III), and Ru(II). Potentially MOCAs can serve
structures of ZIF-8, and the alignment of the nano- 18 MTV-MOF-5–type structures were synthesized as functionalities within MOFs to affect sequence-
crystals was controlled by the anisotropic nature using variously functionalized BDC2– linkers dependent properties. This idea may also manifest
of surface (124). Clearly, the synthesis of nano- [NH2, Br, (Cl)2, NO2, (CH3)2, C4H4, (OC3H5)2, itself in materials recently prepared by the sequen-
crystals, their assembly into larger structures, and and (OC7H7)2]. One of these structures contains tial deposition of multilayer MOF thin films (128).
their incorporation into devices are research areas eight different functionalities in one phase. The It is not always necessary to exercise multiple
of increasing interest. backbone structure (same as MOF-5) is ordered, linkers or specific sequences to acquire hetero-

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whereas functional groups incorporated into the geneity in MOFs without losing either crystallin-
The Materials Beyond framework are varied and disordered. The com- ity or porosity. Recently, microporous MOF-5
At present, MOF chemistry has matured to the point plex arrangements of these functionalities in the materials in which each crystal contains a system
where the composition, structure, functionality, pores can lead to unusual properties; for instance, of mesopores and macropores have been syn-
porosity, and metrics of a metal-organic structure MTV-MOFs showed improved hydrogen and thesized by use of a controlled amount of 4-
can be designed for a specific application. This carbon dioxide uptake capacities relative to MOFs (dodecyloxy)benzoic acid (DBA) to a reaction
precise control over the assembly of materials is
expected to propel this field further into new
realms of synthetic chemistry in which far more
sophisticated materials may be accessed. For ex-
ample, materials can be envisaged as having (i) Self-similarity Complexity
Building blocks
compartments linked together to operate sepa-
1 2 3 4 5
rately, yet function synergistically; (ii) dexterity
to carry out parallel operations; (iii) ability to count,
sort, and code information (7); and (iv) capability
of dynamics with high fidelity (125, 126).
To appreciate how such materials may be
achieved, it is important to step back and consider
the gamut of materials studied thus far. In gen-
eral, crystalline materials are largely composed of
a few building units as constituents of their under-
lying chemical structure. For example, common Materials Beyond
solid-state materials such as zeolites, alloys, poly-
mers, and even MOFs and nanocrystals are each
constructed from one or two kinds of repeating units
(Fig. 5). The same is true for the entire landscape
of human-made crystalline materials. This self-
similarity of structures is quite unlike the heteroge-
neity and multiplicity that characterize biological
molecules. However, the building of materials from
as few as three or four different building units re-
mains an outstanding challenge because such chem-
istry is believed to give mixed phases rather than a
Metals, alloys, silicon, metal oxides, Proteins,
single phase comprising mixed components. zeolites, polymers, MOFs, nanocrystals, ... RNA, DNA, ...
It is our view that vast opportunities exist for
making materials from an increasing number of
unique building units and that a transformative Fig. 5. Crystalline chemical structures of some of the most useful materials. These materials
chemistry is yet to be uncovered for achieving (metals, alloys, silicon, metal oxides, zeolites, and polymers) are constructed from few kinds of building
these materials. This new materials space that is units (one to three) to make largely self-similar materials in which such building units repeat periodically
expected to emerge from linking multiple kinds throughout the material. Few examples exist of synthetic crystals with more than three building units, as
of building units will have unlimited possibilities, found in biological structures (proteins, RNA, and DNA). The linking of building units by strong bonds
especially when the building units are arranged in (reticular chemistry) as exemplified by the construction of MOFs is useful in developing the structure and
specific sequences within crystals. We propose to function space of the “materials beyond.”

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 REVIEW

A D

Zn4O(CO2)6

COOH
X

COOH

MTV-MOF-5

X=H( ), Br ( ), NH2 ( ), NO2 ( ), C4H4 ( ), (CH3)2 ( ), (OC3H5)2 ( ), (OC7H7)2 ( ) MOF-1001

B
2+ 2+
PQT PQT
Metal chelating unit Metallation

Amino acid backbone = Pt(II), = Rh(III), = Ru(II)

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PQT2+/MOF-1001

Resin

2X-

Cl N Cl
Cl Cl N N Cl Cl
Rh Ru2+ Rh
N N N N N N
N N N

O O O

O H O H O H
H2N N N N N N N
Fmoc
O H O H O H

O O O

Cleavage N N N
N N N N N N
Pt+ X- Pt+ X- Pt+ X-
Cl Cl Cl
Metal-organic complex array
(MOCA)

Zn4O(CO2)6

pmg-MOF-5
COOH OC12H25
+

COOH COOH

Fig. 6. Examples of creating heterogeneity within crystalline mate- Heterogeneity within order produced in crystals of MOFs (pmg-MOF-5), where
rials. (A) MTV-MOF-5, in which a heterogeneous mixture of functionalities mesopores and macropores are encased in microporous MOF-5 to give un-
decorates the interior of the crystals to provide an environment capable of usual carbon dioxide capture properties. (D) A MOF (MOF-1001) constructed
highly selective binding of carbon dioxide. (B) Schematic representation of the from linkers having polyether rings, which in themselves create stereoelec-
synthesis of MOCAs, which have a heterogeneity created by arranging metal tronically specific binding of substrate paraquat (PQT2+). Atom colors are as in
complexes in specific sequences to give sequence-dependent properties. (C) Fig. 2; blue polyhedra, Zn. Hydrogen atoms are omitted for clarity.

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1230444-12 30 AUGUST 2013 VOL 341 SCIENCE www.sciencemag.org

The Chemistry and Applications of Metal-Organic Frameworks
Hiroyasu Furukawa, Kyle E. Cordova, Michael O'Keeffe and Omar M. Yaghi

Science 341 (6149), 1230444.

DOI: 10.1126/science.1230444

Strategies for Metal-Organic Frameworks

Metal-organic frameworks are porous materials that can exhibit very high surface areas that have potential for
applications such as gas storage and separation, as well as catalysis. Furukawa et al. (1230444) review the structures
devised so far and discuss the design strategies that allow families of materials to be synthesized and modified with
similar framework topology but vary in pore size and type of functional groups present on the linkers.

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SUPPLEMENTARY http://science.sciencemag.org/content/suppl/2013/08/29/341.6149.1230444.DC1
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