This article was published as part of the

2009 Metalorganic frameworks issue

Reviewing the latest developments across the interdisciplinary area of
metalorganic frameworks from an academic and industrial perspective
Guest Editors Jeffrey Long and Omar Yaghi
Please take a look at the issue 5 table of contents to access
the other reviews.
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Design and synthesis of metalorganic frameworks using metalorganic
polyhedra as supermolecular building blocksw
John J. Perry IV, Jason A. Perman and Michael J. Zaworotko*
Received 23rd October 2008
First published as an Advance Article on the web 3rd March 2009
DOI: 10.1039/b807086p
This critical review highlights supermolecular building blocks (SBBs) in the context of their
impact upon the design, synthesis, and structure of metalorganic materials (MOMs).
MOMs, also known as coordination polymers, hybrid inorganicorganic materials, and
metalorganic frameworks, represent an emerging class of materials that have attracted the
imagination of solid-state chemists because MOMs combine unprecedented levels of
porosity with a range of other functional properties that occur through the metal moiety
and/or the organic ligand. First generation MOMs exploited the geometry of metal ions or
secondary building units (SBUs), small metal clusters that mimic polygons, for the generation
of MOMs. In this critical review we examine the recent (o5 years) adoption of much larger
scale metalorganic polyhedra (MOPs) as SBBs for the construction of MOMs by highlighting
how the large size and high symmetry of such SBBs can aord improved control over the
topology of the resulting MOM and a new level of scale to the resulting framework
(204 references).
1. Introduction
Metalorganic materials, MOMs, (Fig. 1) are comprised of
metal moieties and organic ligands and are exemplied by a
diverse group of discrete (e.g. metalorganic polyhedra,
spheres or nanoballs, metalorganic polygons) or polymeric
structures (e.g. porous coordination polymers, PCPs,
metalorganic frameworks, MOFs, or hybrid inorganicorganic
materials).
Whereas MOMs have existed for several decades
110
it
was not until the early 1990s that they captured broad
attention as it became evident that MOMs are typically
facile to prepare, aesthetically pleasing and, because of
their inherent modularity, prototypal for a diverse range of
structures that are amenable to crystal engineering design
strategies.
1121
The foundation for todays activity in
MOMs resides with the seminal work of A. F. Wells
2225
who introduced the simple and practically useful node and
spacer interpretation of inorganic crystal structures. Inorganic
crystal structures can thereby be described as networks dened
by metal ions (nodes) linked together via bonds (spacer or
edge). An important aspect of this approach is that the
resultant network topology is reliant on the geometry
Department of Chemistry, University of South Florida,
4202 E. Fowler Ave. CHE 205, Tampa, FL 33620, USA.
E-mail: xtal@usf.edu; Fax: +1(813) 974 3203;
Tel: +1(813) 974 3451
w Part of the metalorganic frameworks themed issue.
John J. Perry IV
John J. Perry IV was born
in Tampa, Florida. He
obtained a BA in mathe-
matics and a BA in chemis-
try, graduating with honors
from the University of South
Florida (USF) in 2003.
He has since been working
towards completion of a
PhD degree in chemistry at
USF under the supervision
of Professor Michael J.
Zaworotko. His research
interests include crystal
engineering, supramolecular
chemistry, metalorganic
materials, polyhedra, and mathematical concepts applied to
chemical systems.
Jason A. Perman
Jason A. Perman was born in
Tampa, Florida, and received
his BS degree from the
University of South Florida.
After undergraduate work in
the laboratory of Professor
Michael J. Zaworotko, Jason
joined his research group as a
graduate student in the spring
of 2006. He currently conducts
research in co-crystal con-
trolled solid state synthesis
with emphasis upon new
ligands for new metalorganic
materials.
1400 | Chem. Soc. Rev., 2009, 38, 14001417 This journal is c The Royal Society of Chemistry 2009
CRITICAL REVIEW www.rsc.org/csr | Chemical Society Reviews
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and coordination environment of the nodes as the spacer is
simply a linear connection between adjacent nodes. For
example, if a given metal ion preferably adopts a tetrahedral
geometry and two equivalents of a linear bifunctional ligand
are coordinated to this metal, then a cubic or hexagonal
diamondoid network is the likely outcome (Fig. 2). In a similar
vein, octahedral metals can sustain square grid or octahedral
nets depending upon the metal : ligand stoichiometry (Fig. 2).
Such an approach is inherently modular, meaning that any
existing network structure is in principle prototypal, i.e. it
might serve as a blueprint for the study of the crystallochemistry
of many compounds with the same topology but with a
dierent chemical composition.
2. Foundations
2.1 Design
In the early 1990s, R. Robson
2633
and others
3448
applied the
node and spacer approach to generate coordination polymers,
most typically via coordination of linear ditopic organic
molecules such as 4,4
0
-bipyridyl to transition metal cations.
The resulting compounds can exist as 1-periodic, 2-periodic or
3-periodic nets that are at the very least rational based upon
the geometry of the node and the node : spacer stoichiometry.
0-Periodic structures based upon 4,4
0
-bipyridyl and square
planar metal moieties were developed concurrently.
4951
These
molecular squares and polygons served as precursors to the
Fig. 1 Metalorganic materials encompass discrete as well as extended structures with periodicity in one, two, or three dimensions. The latter
have also been referred to as coordination polymers, metalorganic frameworks, and hybrid inorganicorganic materials.
Fig. 2 Schematic illustration of the node (red) and linear spacer
(blue) approach for design of networks based upon tetrahedral
(above left cubic diamondoid, above right hexagonal diamondoid)
or octahedral metal nodes (below left square grid, below right
octahedral network).
Michael J. Zaworotko
Dr Mike Zaworotko is Pro-
fessor in the Department of
Chemistry at the University
of South Florida, USF.
He was born in Wales in
1956 and received his
BSc and PhD degrees from
Imperial College (1977) and
the University of Alabama
(1982), respectively. He
served at Saint Marys
University, Nova Scotia from
19851998 and joined USF
in 1999. Current research
interests include crystal
engineering, metalorganic
materials, supramolecular chemistry, co-crystals and green
chemistry. Dr Zaworotko has published over 260 peer reviewed
publications and he currently serves as Associate Editor of
Crystal Growth & Design.
This journal is c The Royal Society of Chemistry 2009 Chem. Soc. Rev., 2009, 38, 14001417 | 1401
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metalorganic polyhedra that are discussed below. 3-Periodic
nets such as the diamondoid net were studied
27,5256
through
judicious selection of a tetrahedral metal ion and two
equivalents of a spacer ligand, thereby aording a considerable
degree of predictability and control over the scale and
topology of the resulting compounds. Extension of this crystal
engineering
5765
paradigm across a wide range of metals and
organic ligands created a degree of chemical diversity greater
than that typically encountered in purely inorganic or purely
organic materials and in turn aorded a plethora of prototypal
MOMs. Indeed, given that crystal engineering design
principles are equally applicable to crystals that are sustained
by hydrogen bonds, there are also examples of diamondoid
networks sustained by multiple
6668
(i.e. nodes and spacers) or
single components
6972
(i.e. tectons) that are complementary in
terms of their hydrogen bonding.
2.2 Properties
As the nascent eld of MOMs advanced, the level of complexity
increased and researchers began to address the functionality of
this emerging class of materials. There were early indications
that 3-periodic MOMs could survive guest exchange
73
and, in
the late 1990s, the research groups of O. M. Yaghi and
S. Kitagawa reported the rst examples of MOMs that exhibit
permanent porosity.
74,75
These new materials could aptly be
considered as second generation MOMs for which Yaghi and
Kitagawa coined the terms metalorganic frameworks
(MOFs)
76,77
and porous coordination polymers (PCPs),
respectively.
78,79
Subsequent MOMs possess the lowest densities
and highest surface areas per gram known to mankind.
80,81
Furthermore, many of these MOMs exhibit air/water stability
and thermal stability that is much improved over that of rst
generation MOMs. However, perhaps even more important
than any one particular MOM has been the realization that
such compounds are certainly rational if not predictable in
terms of their structure and porosity. For example, Yaghi and
OKeee developed the versatile and fruitful design strategy
of reticular chemistry,
82
a strategy that exploits secondary
building units (SBUs)
83
as molecular polygons or polyhedra
for the construction of MOFs. An SBU (Fig. 3) is a metal
cluster or molecular complex which is rigid in nature, and,
when the points of extension are considered, prediction of
network topologies that might exist when these molecular
building blocks are linked via polytopic organic linkers is
relatively facile.
As discussed above, rst generation MOMs consist of a
single metal ion node that is linked by polytopic organic
ligands. In this context the use of SBUs to generate porous
MOMs can be viewed as an important evolution in terms of
design and utility because the greater relative size of SBUs
aord much greater surface area and increased pore and cavity
sizes. Additionally, the use of multiple metal ions in a cluster
bridged by multiple coordinating ligands tends to enhance the
robustness of the MOM. SBUs are also important from a
design perspective as they provide a means of controlling the
coordination environment of otherwise promiscuous transition
metals which might be capable of adopting any of several
coordination modes. Thus, the inclusion of SBUs into the
chemists toolbox facilitated rapid development of MOMs
with enhanced properties and structures that can be readily
understood and exploited for design purposes. It should
therefore be unsurprising that interest in MOMs exploded as
their synthetic accessibility was soon combined with a range
Fig. 3 Examples of prototypal secondary building units (SBUs) commonly used in the construction of periodic MOMs. (a.) Cupric acetate is a
dimetal tetracarboxylate square paddlewheel cluster [M
2
(O
2
CR)
4
L
2
] (M = transition metal, L = axial ligand) which mimics a molecular square.
Basic chromium(III) acetate, a m
3
-oxo trimetallic hexacarboxylate cluster [M
3
O(O
2
CR)
6
L
3
] can be used as either a molecular triangle (b.) or a
triangular prism (d.). (c.) Basic zinc acetate is a m
4
-oxo tetrametallic hexacarboxylate cluster, [M
4
O(O
2
CR)
6
], that is prototypal for a molecular
octahedron.
1402 | Chem. Soc. Rev., 2009, 38, 14001417 This journal is c The Royal Society of Chemistry 2009
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of functional properties: unprecedented levels of permanent
porosity;
73,8488
catalysis;
8692
molecular magnetism;
9396
chemical separations and sensing;
97103
luminescence;
104106
and NLO properties
107,108
among others.
109111
Furthermore,
that MOMs are inherently modular and can be generated
through self-assembly means that they are amenable to
ne-tuning of both structure (e.g. scale, functional groups)
and bulk physical properties through either pre-synthetic or
post-synthetic modication.
112122
Indeed, today there is a
general realization that there already exist a plethora of
MOMs that are amenable to control over their structure
property relationships in a manner that was hitherto
unprecedented in materials chemistry. This degree of control
means that the incorporation of more than one useful
property into a single material becomes feasible, i.e.
multi-functional MOMs.
2.3 Discrete metalorganic polyhedra
Notwithstanding the signicant progress that has been made
in terms of de novo design of MOMs, crystal engineering of
MOMs with predictable structures and/or physical attributes
remains a daunting challenge. Indeed, diamondoid nets are
not the only network structures that can occur through linking
tetrahedral moieties since hexagonal diamond (Lonsdaleite)
can also occur.
123
In this vein, design strategies that facilitate
new classes of MOMs with even greater ranges of scale and
control would represent a welcome addition to the eld. This
critical review explores the opportunity represented by
using metalorganic polyhedra (MOPs) as SBBs. Such SBBs
typically start at the nanometre scale and possess high
symmetry, alluding to the possibility of a crystal engineering
strategy for MOMs that combines even greater levels of scale
with highly specic control over topology. Polyhedra are a
geometric construct which have been recognized for millennia
and in recent years they have been used as blueprints for
the design of discrete inorganic,
124132
organic,
133139
and
metalorganic
4951,140152
nanoscale structures. Whereas inorganic
and organic polyhedra are in principle capable of serving as
SBBs, we will focus herein upon metalorganics because they
are so inherently amenable to exterior functionalization.
MOPs can be categorized as follows: Platonic solids,
Archimedean solids, faceted polyhedra and stellated polyhedra.
2.3.1 Platonic MOPs. Perhaps the simplest and most
widely recognized polyhedra are the ve polyhedra
constructed from one type of regular polygon (equal angles
and edge lengths) meeting at identical vertices which are
known as the Platonic solidsthe tetrahedron, hexahedron
(cube), octahedron, dodecahedron and icosahedronall of
which belong to one of the highly symmetric point groups:
tetrahedral, icosahedral, or octahedral (Fig. 4).
There have been several examples of discrete metalorganic
tetrahedra reported in the literature. For example Yaghi et al.
reported a series of isoreticular metalorganic polyhedra
(IRMOP) based upon the common m
3
-oxo centered
Fe
3
O(CO
2
)
6
trimer.
149
Normally this SBU would be regarded
as a triangular prism, but the authors judiciously cap
three cofacial sites with sulfate groups, thereby aording a
triangular SBU with carboxylates oriented 601 from one
another. These molecular triangles are linked by ditopic
bridging ligands such as 1,4-benzene dicarboxylate,
4,4
0
-biphenyl dicarboxylate, tetrahydropyrene-2,7-dicarboxylate,
or 4,4
0
-terphenyldicarboxylate into what the authors refer to
as truncated tetrahedra. Separately, Fujita et al. reported
a number of examples of tetrahedral MOPs based upon
the strategy of molecular panelling.
150152
Fujita coupled
palladium ions with pyridyl based organic ligands designed
to act as molecular triangles, or panels, and his method has
been adopted by several other research groups. Oppel and
Fo cker reported a double walled tetrahedron
153
which was
constructed from another triangular molecule capable of
acting as a ligand with transition metals. Specically they used
a C
3
-symmetric ligand with a triaminoguanidinium core in
combination with zinc or cadmium metal ions to generate
various MOPs.
Another Platonic Solid which is well represented in MOPs is
the hexahedron as exemplied by the cube. Two distinct
strategies have been implemented to generate metalorganic
cubes. In the rst strategy an octahedral metal is complexed to
coordinating ligands chosen so as to terminate along the three
so called exo directions, thus transforming a six coordinate
transition metal into one which is essentially three coordinate
and oriented such that each metal can act as a corner of the
cube. An interesting example of this strategy was described by
Thomas et al. in 1998, where the authors adopt ruthenium
metal ions complexed with [9]aneS
3
and three 4,4
0
-bipyridine
moieties at ca. 901 to one another to act as a single corner of
the cube.
154
This complex was observed to be air and moisture
stable as a solid and dissolved in non-coordinating solvents.
Another example of a metalorganic cube was reported by
Eddaoudi and co-workers,
155
who used a dierent strategy:
in situ blocking of one face of an octahedrally coordinated
metal to form a trigonal pyramidal building unit that can serve
as the corner of a cube. They implemented the strategy with
nickel ions and a bidentate bridging moiety, 4,5-imidazoledi-
carboxylic acid, that chelates to Ni ions in a fac-octahedral
fashion. The resulting anionic metalorganic cube exhibits a
distance from the center of the cavity to a non-hydrogen atom
of the imidazole ring of ca. 4 A

, aording a small cavity of

B50 A

3
with T
h
symmetry.
Chan et al. investigated the use of a tridentate ligand
capable of acting as the trigonal pyramidal corner of
a cube when combined with either square-planar or
octahedral metal ions. Specically, they reported the
synthesis of a neutral, O
h
-symmetric cube from Ni
2+
metal
ions and 2,4,6-tri[(4-pyridyl)sulfanylmethyl]-1,3,5-triazine in
dimethylformamide.
156
The pyridyl groups of eight ligands
coordinate equatorially with chloride ions in the axial
positions. The square-planar geometry of the metal centers
with respect to the bridging ligands occurs at the center of
the six faces of the cube, with the pyridyl pendant arms of the
ligands expanding diagonally along this face toward the
corners of the cube and the center of the ligand.
Finally, the octahedron represents a Platonic solid that
has been well explored in terms of MOPs. An aesthetically
pleasing example of an octahedral MOP was reported by
Eddaoudi and co-workers
157
when they bridged 6 indium(III)
metal ions with 12 2,5-pyridinedicarboxylate ligands that
This journal is c The Royal Society of Chemistry 2009 Chem. Soc. Rev., 2009, 38, 14001417 | 1403
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exhibit both chelating and bridging coordination modes. The
six metal ions reside on the vertices of an octahedron, while the
ligands generate the edges. The resulting triangular windows
open the inner cavity of the octahedron, which in the single
crystal X-ray structure holds a single ethanol molecule. The
isolated MOP is anionic and adopts T
h
symmetry and
1,2-diammoniumcyclohexane cations serve as bridges by
linking the octahedra via hydrogen bonding into a 3-periodic
network.
2.3.2 Archimedean MOPs. A class of polyhedra that are
closely related to Platonic solids are the Archimedean solids, i.e.
geometrical structures generated from a single type of vertex
for which all of the faces are regular polygons. However,
unlike the Platonic solids there are at least two dierent
faces in each Archimedean polyhedron making them
semiregular solids. There are 15 Archimedean solidsthe
truncated tetrahedron, cuboctahedron, truncated cube,
truncated octahedron, rhombicuboctahedron, snub cube
(plus enantiomer), icosidodecahedron, truncated cuboctahedron,
truncated dodecahedron, truncated icosahedron, rhombicosi-
dodecahedron, snub dodecahedron (plus enantiomer), and
truncated icosidodecahedrontwo of which, the cuboctahedron
and icosidodecahedron, are also constructed from a single type
of edge and sometimes referred to as quasiregular. Archimedes
described 13 convex polyhedra constructed from two or more
types of regular polygons that meet at identical vertices. These
Archimedean solids (Fig. 4) are therefore distinct from Platonic
solids, which are composed of one type of polygon meeting in
identical vertices, and from the Johnson solids, whose regular
polygonal faces do not meet in identical vertices.
Fig. 4 Platonic and Archimedean solids. First row (left to right): tetrahedron, hexahedron (cube), octahedron, dodecahedron, and icosahedron.
Second row: truncated tetrahedron, cuboctahedron, truncated cube, truncated octahedron, and rhombicuboctahedron. Third row: truncated
cuboctahedron, snub cube, icosidodecahedron, and truncated dodecahedron. Fourth row: truncated icosahedron, rhombicosidodecahedron,
truncated icosidodecahedron, and snub dodecahedron.
1404 | Chem. Soc. Rev., 2009, 38, 14001417 This journal is c The Royal Society of Chemistry 2009
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There are numerous examples of organic or metalorganic
polyhedra that would be considered Archimedean in nature,
i.e. composed of two or more dierent molecular polygons.
Stang et al. reported a series of what can best be described as
truncated tetrahedra (the simplest and most common
Archimedean MOP).
142,158
In their method, the authors
adopt face-directed self-assembly of tritopic ligands such as
tris(pyridylethynyl)benzene or tris(p-cyanophenylethynyl)-
benzene with cis-platinum or cis-palladium bistriate salts.
The resulting Archimedean MOPs were studied via solution
NMR experiments and single crystal X-ray diraction. In each
structure six Pd
2+
or Pt
2+
ions self-assemble with four ligands
in such a manner that the metal ions act as the vertices and the
tritopic moieties act as the triangular (truncated) faces of
the truncated tetrahedron. Another example of a truncated
octahedron was provided by Yaghi and co-workers.
159
In this
MOP, a dicarboxylate ligand with an angle of ca. 901 between
the carboxylate groups was employed to generate dimetal
tetracarboxylate square paddlewheel SBUs, six of which were
linked together. The location of the metal cluster coincides
with the vertices of an octahedron and the authors referred to
their compound (MOP-28) as a truncated octahedron.
Stang and co-workers reported
160
cuboctahedra that are
constructed through self-assembly of 20 tridentate and bidentate
subunits to transition metals. In one example a triangular
tridentate ligand, 1,3,5-tris(4
0
-Pt(PPh
3
)
2
OSO
2
CF
3
)ethynylbenzene,
and a bidentate ligand, 4,4
0
-bispyridylacetal, were used.
In another example, 1,3,5-tris(4-pyridylethnynyl)benzene was
combined with bis(4-[trans-Pt(PPh
3
)
3
OSO
2
CF
3
]phenyl)-
ketone. Both spheroids were characterized in solution via
electrospray mass spectrometry and NMR and were estimated
to be ca. 5 nm in diameter. Fujita et al. reported a series of
MOP compounds that are of a roughly spherical shape
and possess the symmetry of the cuboctahedron.
161
These
compounds are based upon palladiumpyridyl chemistry and
demonstrate a wide range of modularity; simple functionalization
of the bis(4-pyridyl)-bent ligand can lead to endohedral
functionalization of the inner cavity of the spheroid. The
ligand has a built-in angle of B1201 subtended between
pyridyl groups which coordinate to Pd
2+
ions in a square-
planar fashion. In addition to being amenable to functionalizing
the inner cavity, this MOP can be scaled-up by adopting
expanded ligands that retain the bis-pyridyl moieties and
the 1201 angle, i.e. this MOP is prototypal for a series of
isoreticular structures.
Organic MOPs also exist as exemplied by the 1997 report by
Atwood and MacGillivray of an organic, hydrogen bonded
version of an Archimedean snub cube.
162
In this spheroid, six
calix[4] resorcinarenes are combined with 8 water molecules
through 60 OH O hydrogen bonds to form a hydrogen
bonded capsule that is closely related to the snub cube. This
compound is stable in apolar organic solvents and has been
investigated via single crystal X-ray diraction and
1
H NMR
spectroscopy. The hollow interior of the spheroid is capable of
encapsulating guests with its internal volume cavity of B1375 A

3
.
2.3.3 Faceted MOPs. A third class of discrete polyhedron
that is particularly salient to MOMs are those faceted
polyhedra that are sustained by vertex sharing of polygons
rather than the edge sharing observed in Platonic and
Archimedean solids. These nonconvex uniform polyhedra
dier from the convex, edge-sharing versions in that they
necessarily contain both closed faces (i.e. the polygon) and
open windows to the interior of the spheroid (Fig. 5). There
are nine examples of faceted polyhedra derived from
regular convex polygonal facesthe tetrahemihexahedron,
octahemioctahedron, and small icosihemidodecahedron are
constructed from triangles alone; the cubohemioctahedron,
small rhombihexahedron, and small rhombidodecahedron are
formed from squares alone; the small cubicuboctahedron is
constructed from a combination of triangles and squares; the
small dodecicosidodecahedron is generated from triangles and
pentagons; while the small dodecahemidodecahedron is
fashioned from the intersection of pentagons alone.
Of the nine faceted polyhedra, the three that can be generated
via vertex-linking of squares represent especially viable
stargets for MOPs as square paddlewheel SBUs (Fig. 3a) are
ubiquitous in coordination chemistry. The only dierence
between these three polyhedra is the angle subtended by the
vertices, a parameter that can be controlled by the synthetic
chemist when a ligand is chosen to link the square SBUs. The
cubohemioctahedron, small rhombihexahedron and small
Fig. 5 Faceted polyhedra. First row (left to right): tetrahemihexa-
hedron, octahemioctahedron, and small icosihemidodecahedron.
Second row: cubohemioctahedron, small rhombihexahedron, and small
rhombidodecahedron. Third row: small dodecahemidodecahedron,
small cubicuboctahedron, and small dodecicosidodecahedron.
204
Fig. 6 The three faceted polyhedra that arise from vertex linking of
squares only: (a) cubohemioctahedron; (b) small rhombihexahedron;
(c) small rhombidodecahedron.
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rhombidodecahedron possess 12, 24, and 60 vertices, respectively
(Fig. 6), with the small rhombihexahedron, which has also
been termed a nanoball, of particular interest since the angle
between its vertices is 1201, i.e. it corresponds exactly to the
angle subtended by meta-substituted benzene rings. As such it
has been extensively studied by several research groups and it
can be regarded as the prototypal example of a metalorganic
faceted polyhedron.
163,164
The rst such example was constructed from 12 dimetal
tetracarboxylate square paddlewheel complexes, M
2
(bdc)
2
L
2
(M: Cu(II); bdc: 1,3-benzene dicarboxylate and L: solvent
molecules or pyridine-type bases), vertex linked at 1201 by
the bdc ligands. The versatility of this nanoball is such that
multiple derivatives have been reported
165168
(Fig. 7). The
hydroxylated version of the nanoball has been studied in
solution
169,170
and forms polymer composites
171,172
whereas
the dodecyloxy derivative incorporates into a lipid membrane
and has been studied as a synthetic ion channel with selectivity
for smaller alkali metal cations.
173
The small rhombihexahedron
shares the same edge skeleton as the Archimedean solid
known as the cuboctahedron and these terms have been used
interchangeably in the context of MOMs since the edge
skeleton denes the connectivity.
MOPs that can be described as small cubicuboctahedra have
also been characterized. In 2006, Sun and co-workers
reported
174
a MOP constructed from Cu(ClO
4
)
2
6H
2
O and
benzene-1,3,5-triacetic acid. Eight carboxylate ligands bind to
11 Cu
2+
ions to form 5 square paddlewheel SBUs and one
mono-copper complex that adopts a square-planar geometry.
The triangular benzene-1,3,5-triacetate ligands are linked to
the ve square paddlewheel SBUs and the mono-copper
moiety. The resulting MOP can therefore be regarded as six
square moieties bridged by eight triangles, i.e. it is a small
cubicuboctahedron. In 2008, Sun et al. reported
175
a related
structure based upon a dierent triangular ligand, N
0
,N
00
,N
0 0 0
-
tris(pyrid-4-ylmethyl)-1,3,5-benzenetricarboxamide. In this
instance the authors chose a dierent copper salt,
Cu(BF
4
)
2
6H
2
O, and the coordination is dierent from the
previous example in that pyridyl ligands coordinate to Cu
2+
in
a square-planar fashion, but the MOP geometry remains the
same: triangular ligands linked at their vertices to the square
metalligand complexes so as to form what can be considered
a small cubicuboctahedron.
Another example of a faceted polyhedron was recently
reported by Mattay et al.
176
In this contribution the authors
describe a cavitand-terpyridine subunit which can be viewed as
Fig. 7 The nanoball family portrait. Discrete nanoballs are based upon 12 paddlewheel SBUs and are therefore constructed from 24 Cu
2+
ions
and 24 isophthalate molecules. A number of decorated nanoballs based upon substitution at the 5-position of the isophthalate ligands have been
crystallographically characterized.
1406 | Chem. Soc. Rev., 2009, 38, 14001417 This journal is c The Royal Society of Chemistry 2009
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a molecular square. When combined with a zinc salt,
[Zn(NCMe)
6
](tetrakis(3,5-bis(triuoromethyl)phenyl)borate)
2
,
in a 1 : 2 ratio of cavitand-to-metal, a cuboctahedron MOP in
which six cavitands are bridged by nearly linear Znterpyridine
linkages is formed. This MOP has been studied via ESI-MS,
small angle X-ray scattering (SAXS), diusion NMR spectro-
scopy, and elemental analysis. However, no single crystal
X-ray structure was obtained. The authors assigned structure
based upon the aforementioned analyses and molecular
modeling. The predicted structure exhibits an outer diameter
of ca. 4.6 nm with large windows of ca. 0.77 nm that provide
access to an inner cavity of volume ca. 13.7 nm
3
.
2.3.4 Stellated MOPs. A fourth class of polyhedron that
has been exploited are the stellated polyhedra, in particular the
stella octangula.
177
This MOP was rst reported by Hardie
et al. and is constructed via self-assembly of naked Pd
2+
ions and a derivative of a cyclotriveratrylene (CTV) macro-
cyclic host molecule. The authors exploited the rigid and
curved nature of the CTV derivative to impart molecular
recognition and increase the inner cavity volume over that of
a at ligand counterpart. The bowls of the CTV ligands, which
occupy the eight triangular faces of an octahedron, orient
toward the inner cavity of the MOP with their rigid pyramidal
portions pointed outward away from the center. This is
why the authors interpret their structure not as a simple
octahedron, but rather a stellated version in which all of the
edges encompassing each face of the octahedron are extended
outward until they meet at a point away from that face,
generating a star-like prism. Each of these discrete stella
octangula is composed of six Pd
2+
ions located at the vertices
of a simple octahedron, with eight C
3
-symmetric ligands based
upon the macrocycle, and results in an overall cationic com-
pound, which in this case is counter-balanced with nitrate ions.
The stella octangula are chiral and each individual complex is
composed of identical homochiral ligands. However, the bulk
solid exists as a racemic mixture. These MOPs were studied via
single crystal X-ray diraction,
1
H NMR, ESI-MS, and
diusion ordered NMR spectroscopy (DOSY). The size
(ca. 3.1 nm) and octahedral symmetry of the complexes in
solution was thereby conrmed.
In principle, the aforementioned MOPs represent a toolbox
of SBBs for the construction of both low connectivity and high
connectivity nets. This contrasts with SBUs that are by their
geometric nature typically limited to the generation of 2-, 3-, 4-
and 6-connected nets. Furthermore, MOPs exhibit potential
for decoration around their periphery and therefore for
serving as an SBB through either cross-linking at exterior
metal sites or via cross-linking through the ligand (e.g. the
use of a tetracarboxylato ligand rather than a dicarboxylato
ligand). The remainder of this review addresses the use of such
MOPs and SBBs.
3. MOFs from MOPs: frameworks sustained by
supermolecular building blocks
For the purpose of this review we shall dierentiate between
frameworks with polyhedral cages
178
which share faces and
those constructed via polyhedral SBBs. In the case of the
former, HKUST can be considered an archetype.
179
HKUST
is constructed from Cu
2+
and trimesic acid in a 3 : 2 ratio with
the dicopper square paddlewheel SBU joining. HKUST
contains a nanoball but it is not isolated since it shares its
12 faces with additional nanoballs (Fig. 8). The nanoball does
not participate as a node but rather it can be regarded as an
assembly of 4- and 3-connected SBUs that generate void space
in a framework that exhibits a tbo topology. This review
focuses upon frameworks for which polyhedra serve as SBBs
via linking through multi-topic ligands rather than the sharing
of polygonal faces. One might view this situation as a natural
extension of the existing hierarchy: an SBB sustained
framework can be regarded as being constructed of nanoscale
MOPs; MOPs are constructed from SBUs; SBUs are
comprised of metal ions bridged by organic ligands. However,
whereas from the perspective of properties there might be a
greater level of complexity, from a design perspective the
bigger the SBB, the more likely that there will be a high level
of symmetry and a more limited number of topological
possibilities. Therefore, one might rationalize SBBs as simply
an extension to the SBU approach that facilitates a larger
length scale and a greater control over topology. The former is
obvious and consequential: the larger the building block one
exploits, the larger must be the resultant framework which in
turn means that even interpenetrated structures
180182
might
exhibit meaningful porosity. The latter is perhaps not quite so
obvious but it is also consequential. The SBB approach
provides a toolbox of building blocks capable of acting as
nodes with rare or even unprecedented connectivity since MOPs
oer coordination numbers higher than those possible with
simple inorganic metal clusters or molecular complexes.
Furthermore, that SBBs are designed from rst principles
means that one might control or even customize the nature of
the resulting cavities (size, shape, and chemical functionality).
3.1 Platonic solids
3.1.1 Tetrahedra/supertetrahedra. Tetrahedra and super-
tetrahedra represent perhaps the earliest and most widely
studied SBBs. Yaghi et al. recently reported MOF-500
183
([1], Table 1), a framework which is conceptually based
upon the linking of tetrahedra, and they also established
a synthetic method for the synthesis of metalorganic
tetrahedra composed from iron trimers based upon a trigonal
prismatic SBU (Fig. 3b and d). These tetrahedra (IRMOP
5153)
149
are synthesized from Fe
2
(SO
4
)
3
in a solution of
Fig. 8 HKUST: sharing the same polygonal (SBU) face between
polyhedrons (shown here with small rhombihexahedrons) diers from
the SBB approach.
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N,N
0
-dimethylformamide and triethylamine in the presence
of 4,4
0
-biphenyldicarboxylate and pyridine. Trigonal
[(Fe
3
O)(CO
2
)
3
(SO
4
)
3
] units are coordinated to three terminal
pyridine ligands. MOF-500 is built from these tetrahedral
SBBs by replacing the terminal pyridine groups with cis-1,2-
bis-4-pyridylethane, a ditopic bridging ligand capable of
linking the tetrahedra together. The resulting network exhibits
four dierent interconnected pores that are generated from
four types of porous tetrahedral SBBs with free pore diameters
ranging from 5.2 to 18.0 A

. The solvent accessible free volume

of MOF-500 is B78% which is occupied by guests including
eight dimethylammonium cations that balance the charge of
the anionic framework. The arrangement of the tetrahedral
SBBs in MOF-500 aords b-cristobalite (SiO
2
) topology.
3.1.2 Hexahedra (cubes). MOPs exhibit several examples
of structures which can be regarded as cubes. Indeed, several
authors have chosen to adopt the nomenclature metalorganic
cubes (MOC), however such terminology can be ambiguous
since it does not necessarily address the ne details of the MOP
and its constituent parts. Nevertheless, such MOPs are capable
of serving as SBBs such as those rst reported by Eddaoudi
and co-workers in 2004.
155
This cube is constructed from Ni
2+
ions and 4,5-imidazoledicarboxylic acid (Fig. 9), is anionic and
has the formula [Ni
8
L
12
]
20
(H
3
L = 4,5-imidazoledicarboxylic
acid). The 8 Ni
2+
ions reside at the vertices of a cube and
are linked through 12 L ligands which coordinate in a
bis-chelating fashion.
These cubes were subsequently investigated by other
research groups and incorporated into framework MOMs.
In 2005, Xu and co-workers reported the assembly of
these cubes into a framework via bridging with Na
+
cations
([2], Table 1).
184
In Xus structure, the authors report that the
ligand is fully deprotonated (in contrast with the structure
reported by Eddaoudi) due to the use of a strong base, sodium
hydroxide. Two types of cavity were observed: the cavity of
the cube itself; a cavity generated by the linking of the cubes
into a 3-periodic array. The distance from the center of the
cube to the closest non-hydrogen atom of the imidazole ring is
3.236 A

and the inner cavity of the cube exhibits a volume of

ca. 52 A

3
. The second cavity has a larger volume (B80 A

3
) as
the distance from the center to the closest Na
+
is 3.717 A

. The
authors reported a BET surface area of 147 m
2
g
1
and a
micropore volume of 0.26 cm
3
g
1
obtained from nitrogen
adsorption isotherms. In a separate contribution, Xu also
reported a related 3-periodic MOM in which the Ni cubes
are bridged by Li
+
ions in lieu of sodium cations ([3],
Table 1).
185
This structure is also porous with similar BET
surface area and micropore size (145 m
2
g
1
and 0.28 cm
3
g
1
,
respectively).
Gao et al. reported a dierent strategy for the use of
4,5-imidazolate cubes as building blocks for higher order
structures.
186
They reported a variation of the cube that
incorporates Co rather than Ni ([4], Table 1). The Co cations
are mixed-valent, six Co
III
and two Co
II
, thereby aording an
anion of formula [Co
8
L
12
]
14
. The authors envisioned using
the cubes as metalloligands for generation of extended
structures through either hydrogen bonding or coordination
to cationic molecular complexes and they reported a
crystal structure involving [Co
8
L
12
]
14
, [Ni(cyclam)]
2+
and
[Ni(cyclam)(H
2
O)
2
]
2+
. In the crystal lattice each cube interacts
with two [Ni(cyclam)]
2+
cations along the b-axis through axial
coordination to two oxygen atoms diagonally across from one
another in the cube, resulting in a 1-periodic coordination
polymer along this direction (Fig. 10). Additionally the
cubes are involved in hydrogen bonding with two sets of
Table 1 A tabulation of MOMs derived from SBBs. Topology can be ambiguous depending upon how MBBs and SBBs are dened
Compound SBU Type SBB Type Topology Metal Ligand Author (ref. #)
[1] Trigonal prismatic Tetrahedron SiO
2
(b-cristobalite) Fe(III) Carboxylate and dipyridine Yaghi
183
[2] Square Cube Not determined Ni(II) 4,5-Imidazoledicarboxylate Xu
184
[3] Square Cube Not determined Ni(II) 4,5-Imidazoledicarboxylate Xu
185
[4] Square Cube 1-Periodic chains Co(II/III) 4,5-Imidazoledicarboxylate Gao
186
[5] Square Octahedron pcu-a Cu(II) Pyridines Lah
188
[6] Square Cubohemioctahedron fcu (nbo) Co(II) Tetracarboxylate Yaghi
190
[7] Square Cubohemioctahedron fcu (nbo) Ni(II) Tetracarboxylate Eddaoudi/
Zaworotko
191
[8] Square Cubohemioctahedron fcu (nbo) Co(II) Tetracarboxylate Eddaoudi/
Zaworotko
191
[9] Square Cuboctahedron fcu Cu(I) Cyano Huang
193
[10] Square paddlewheel Nanoball 1-Periodic chains Cu(II) Methoxycarboxylate Zaworotko
194
[11] Square paddlewheel Nanoball bcu-a Cu(II) Sulfonatocarboxylate Zaworotko
194
[12] Square paddlewheel Nanoball pcu-a Cu(II) Tetracarboxylate Zaworotko
196
[13] Square paddlewheel Nanoball pcu-a Cu(II) Tetracarboxylate Zhou
197
[14] Square paddlewheels/
triangles
Nanoball rht Cu(II) Tetrazolecarboxylate Eddaoudi/
Zaworotko
200
[15] Square paddlewheel Nanoball rht Zn(II) Carboxylate Lah
202
[16] Square paddlewheel Nanoball rht Cu(II) Carboxylate Schro der
203
Fig. 9 An example of a discrete metalorganic cube consisting of 12
bis-chelating ligands around 8 metal cations occupying the vertices of
the cube.
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[Ni(cyclam)(H
2
O)
2
]
2+
ions along the ac plane, leading to an
overall 3-periodic network if hydrogen bonding is taken into
consideration.
3.1.3 Octahedra. Lahs group reported a face-driven
corner-linked polyhedron with C
3
-symmetric ligands and C
4
-
symmetric metals, a truncated octahedron [Pd
6
L
8
]
12+
(Fig. 11).
187
The ligand N,N
0
,N
00
-tris(3-pyridinyl)-1,3,5-benzene-
tricarboxamide can adopt conformational isomers and
aorded two polyhedra when crystallized: the syn-conformer
with cavity volume ca. 1600 A

3
and the anti-conformer with a
cavity volume of ca. 1900 A

3
. NMR studies suggest that the
syn-conformer polyhedron dominates in solution. The stability
of these materials in dimethyl sulfoxide was addressed via
ESI-MS experiments that indicated a molecular weight of
4.8 kDa.
If the typical square planar metal is switched to an octahedral
metal such as Cu
2+
with the same ligand and a dierent
4-pyridinylmethyl version of the ligand then an augmented
primitive cubic net ([5], Table 1) is generated because counter
nitrate ions link the copper vertices (Fig. 12).
188
Two-fold
interpenetration of these nets is observed with pp interactions
between the central benzene moieties of the ligands in adjacent
nets. Perchlorate counterions aorded an unusual cluster of
octahedra which resembles the chair form of cyclohexane
(Fig. 13).
3.2 Archimedean solids
3.2.1 Cuboctahedron (cubohemioctahedron). We have thus
far presented examples of four and six connected SBBs that
aord regular nets with transitivity 1111. An additional tiling
with transitivity 1112 is feasible with a polyhedron resembling
a cubohemioctahedron, also referred to as a cuboctahedron,
that is constructed from one type of edge and one type of
vertex 3.4.3.4.
189
Such a polyhedron possesses 12 vertices and
may serve as a node if linked in such a manner that an
augmented face center cubic motif is generated. Three such
metalorganic networks have been generated through the use
of a tetracarboxylate ligand and either Co
2+
or Ni
2+
([6], [7],
[8], Table 1).
190,191
Six square faces meeting at 901 angles are
required from the metalligand coordination and the resulting
cubohemioctahedron is necessarily anionic when constructed
from M(II) and bdc: [M
6
(bdc)
12
]
12
. This SBB is an exception
to the others discussed herein since it has yet to be reported as
a discrete moiety (Fig. 14).
Fig. 10 Chains of metalorganic cubes linked through Ni
2+
cyclam
cations.
Fig. 11 Discrete metalorganic octahedron with blue faces representing
C
3
-ligands and green vertices representing metal ions.
Fig. 12 An augmented primitive cubic net constructed from metal
organic octahedra that are linked via nitrate anions at the six vertices.
Fig. 13 Metalorganic octahedra behaving as a ditopic SBB joined
through perchlorate anions into a cyclohexane-like motif.
Fig. 14 An anionic metalorganic cubohemioctahedron constructed
from 12 isophthalate molecules and 6 M
2+
ions.
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The SBU that sustains the SBB contains two crystallo-
graphically independent metal ions which exhibit distorted
octahedral geometry. The interior metal of the cubohemi-
octahedron SBB coordinates to four monodentate carboxylato
oxygen atoms in the equatorial positions and aqua ligands
in the axial sites. The two carboxylato ligands of bdc are
monodentate and aord an angle of B901. Additional metal
ions neutralize the charge of the ca. 1.8 nm SBB and are
coordinated to the exterior of the SBBs through an aqua
ligand and two of the four monodentate carboxylates
(Fig. 15 and 16). Three related MOMs were synthesized in
the presence of N,N
0
-dimethylformamide and water, either
solvothermally or by slow diusion with the reactants.
The MOMs exhibit the same fcu topology (NbO net
when treating the metal and ligand as quadrilateral building
blocks), but a dierent scale because of the length of
the tetracarboxylate ligands; biphenyltetracarboxylate
4
,
azobenzenetetracarboxylate
4
and benzoimide phenanthroline
tetracarboxylate
4
(BIPA-TC
4
) (Fig. 17). In all three
structures, six cubohemioctahedra join at their square
faces so as to generate an octahedral cavity large enough to
accommodate 2700 A

3
, 5600 A

3
and 36 000 A

3
spheres,
respectively. The biphenyltetracarboxylate structure converts
from the square SBU to a tetrahedral SBU after prolonged
exposure to heat under mother liquor, thereby transforming
from an NbO net into a PtS net with reduced pore volume.
190
The other two MOMs constructed from the cubohemioctahedral
SBB and tetracarboxylate ligands adsorb gases and exchange
metal cations from solution without loss of crystallinity.
191
The cuboctahedron is not limited to carboxylate based
materials and has been observed in several inorganic clusters
as exemplied by a structure that is sustained by a m
4
-S
coordination with Cu(I) (Fig. 18).
192
Huang et al. generated
a face centered cubic net (fcu) from a cuboctahedral SBB
constructed from [Cu
12
(m
4
-SCH
3
)
6
]
6+
using CN

ligands as
connectors between the copper vertices of the SBBs ([9],
Table 1).
193
The vertices of the cuboctahedron are occupied
by twelve Cu(I) cations with sulfur atoms occupying the
centers of the six square faces. The fcu net does not form
under mild conditions, CuCl and cysteamine hydrochloride
aord a 4
4
-net. Rather, it is generated under solvothermal
conditions (1401 C to 160 1C) that facilitate in situ synthesis
of both SCH
3

(from NaSCN and methanol) and CN

(from either NaSCN or acetonitrile). The octahedral cavity

generated from six linked SBBs can only accommodate a sphere
of volume ca. 90 A

3
because methyl moieties extend into the
cavity. The solvent that occupies the tetrahedral and octahedral
cavities can be removed at elevated temperatures and the
resulting anhydrous material remains stable until 190 1C.
3.3 Faceted polyhedra
3.3.1 Nanoballs (truncated cuboctahedra). The prototypal
nanoballs of formula [Cu
2
(bdc
2
)L
2
]
12
were rst reported as
discrete MOMs in 2001 and their development as SBBs
followed shortly thereafter when decorated versions of the
Fig. 15 The SBU for the metalorganic cubohemioctahedron
consists of two metal cations (Ni
2+
or Co
2+
) coordinated to four
carboxylato ligands.
Fig. 16 Face centered cubic (fcu) representation of the network
sustained by 12-connected metalorganic cubohemioctahedra.
Fig. 17 The biphenyltetracarboxylic acid (left), azobenzenetetracarboxylic acid (center) and benzoimide phenanthroline tetracarboxylic acid
(right) ligands used in the synthesis of metalorganic cubohemioctahedron-based fcu-like nets.
Fig. 18 The metalorganic cuboctahedron SBB built with m
4
-
coordinated sulfur atoms (gold) and copper atoms (green).
1410 | Chem. Soc. Rev., 2009, 38, 14001417 This journal is c The Royal Society of Chemistry 2009
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nanoballs were isolated (Fig. 7). Such decoration can occur at
either of two sites on the nanoball: (i) the vertices, by
decorating the 5-position of the bdc ligand; (ii) via ligand
coordination at the center of the square faces (Fig. 19), i.e. the
exterior apical position of the tetracarboxylate paddlewheel
SBUs. Zaworotko et al.
194
reported the rst such structures in
2004 and referred to their structures as being examples of
suprasupermolecular chemistry,
195
thereby emphasizing the
controlled use of nanoscale nodes (the nanoball) to generate
extended coordination polymers (MOMs). A consequence of
the size of the nanoballs is the existence of up to 36 peripheral
sites for decoration. However, not all sites need to or should be
used since, although the ideal symmetry of the nanoball is O
h
,
cross-linking can exploit only some decoration sites, thereby
resulting in lower levels of connectivity.
3.3.1.1 Chains of nanoballs. In principal every bdc ligand
might generate a nanoball although bdc ligands without
substituents in the 2-, 4- and 6-positions are preferred since
they are not as likely to sterically inuence the torsion angle
between the carboxylate moieties. Zaworotko et al.
194
reported that layering a solution of 5-methoxy-isophthalic
acid and 2,6-lutidine dissolved in methanol over a solution
of Cu(NO
3
)
2
dissolved in methanol and nitrobenzene resulted
in nanoballs that could be described as being the result of
self-assembly of 70 species (24 Cu
2+
ions, 24 5-MeO-bdc
ligands and 22 MeOH/H
2
O coordinated to 22 of the 24 axial
sites). The resulting nanoball exhibits a volume of B11.5 nm
3
and participates as a node in a chain of nanoballs ([10],
Table 1) because two methoxy groups on each nanoball
coordinate to Cu
2+
moieties on adjacent nanoballs
(Cu O
methoxy
2.26 A

) (Fig. 20).
3.3.1.2 bcu nets of nanoballs. Zaworotko et al. reported how
a methanol solution of the sodium salt of 5-sulfoisophthalic
acid and Cu(NO
3
)
2
layered over a methanol solution of
4-methoxypyridine aorded a decorated anionic nanoball
sustained by 5-sulfonato-bdc ligands.
194
The crystal structure
revealed that the nanoballs form an anionic body centered
cubic (bcu) net with nanoball nodes that are approximately
3.6 nm in diameter ([11], Table 1). The overall symmetry was
reduced to this level because 16 of the 24 sulfonates from
5-SO
3
-bdc pair with 8 [Cu(methoxypyridine)
4
]
2+
cations to
crosslink the nanoballs (Fig. 21). The cavities contain 4-meth-
oxypyridinium cations and [Cu(methoxypyridine)
4
(H
2
O)
2
]
2+
cations, thereby balancing the framework charge.
3.3.1.3 pcu nets of nanoballs. In 2007, Zaworotko and
co-workers reported a pcu-like net built from nanoball SBBs
([12], Table 1).
196
Whereas the nanoball chains and the
nanoball bcu-like nets discussed above arise via coordination
bonds, this new pcu-like net was generated by covalent
cross-linking of the bdc ligands. An appropriate strategy for
such cross-linking of nanoballs involves the design of
tetracarboxylato ligands that are formed by linking at
the 5-position of bdc. Zaworotko et al. synthesized such a
Fig. 19 The metalorganic nanoball is modular in that it can be
functionalized at either the vertices (gray extension) or the square faces
(gold extensions).
Fig. 20 2-Connected nanoballs. A methoxy oxygen atom on a 5-MeO isophthalate ligand coordinates to the axial position on a dicopper
paddlewheel from an adjacent nanoball to form chains.
Fig. 21 Metalorganic nanoballs are cross-linked to eight adjacent
nanoballs through two coordinate covalent cross-links represented by
the gold rods thereby sustaining a bcu-like topology.
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tetracarboxylic acid with a exible aryloxy linkage, 1,3-bis(5-
methoxy-1,3-benzene dicarboxylic acid)benzene (Fig. 22).
Reaction of this ligand with Cu(NO
3
)
2
in a dimethyl
sulfoxide solution of o-dichlorobenzene and pyridine at
115 1C for 24 hours aorded blue-green prismatic crystals.
Single crystal X-ray crystallography revealed that the exibility
of the ligand facilitated quadruple cross-linking, i.e. each
nanoball is cross-linked with six adjacent nanoballs through
four bridging ligands (Fig. 23).
The authors noted that four-fold cross-linking is feasible in
two modes: via all six of the open windows aording local
O
h
symmetry; through two open windows and four square
faces aording local D
4h
symmetry. The nanoball nodes cross-link
in the latter fashion and the compound crystallized in the
tetragonal space group I422. The ligand adopted two crystallo-
graphically independent orientations: a syn-conformation
aording a cylinder of dimensions B7.24 A

(Cu Cu from
SBU) 10.54 A

(centroidcentroid of the bridging aryloxy

groups); an anti-conformation generating a cylinder of
dimensions B5.86 A

(oxygen atoms that start the bridge)

17.88 A

. The rst cylinder is oriented along the a- and b-axes

and is lled with solvent molecules whereas the second
cylinder is oriented along the c-axis and results in a persistent
void that becomes a channel along this direction (Fig. 24). The
network contains large cavities of ca. 18.3 A

along the
a,b-axes and 13.56 A

along the c-axis. Unfortunately 2-fold

interpenetration mitigates this 1.8 1.8 1.4 nm cavity.
Zhou and co-workers utilized 5,5
0
-methylene-diisophthalic
acid (Fig. 25) and Cu
2+
to synthesize another 3-periodic
framework constructed from linking nanoballs into a pcu-like
network ([13], Table 1).
197
Nanoballs are cross-linked to six
others along three orthogonal directions through four
bridging ligands. The authors identify the network as being
related to 3.4
4
, or the linking of rhombicuboctahedra and
squares.
198
This pcu net does not exhibit interpenetration,
presumably due to the shorter length of the bridge between
Fig. 22 1,3-Bis(5-methoxy-1,3-benzene dicarboxylic acid)benzene, a
exible tetracarboxylate ligand.
Fig. 23 Illustration of the pcu-like topology of the quadruple cross-
linked metalorganic nanoball structure. Each nanoball is cross-linked
to six adjacent nanoballs through four covalent cross-links represented
by the purple cubes.
Fig. 25 5,5
0
-Methylene-diisophthalic acid.
Fig. 24 (a.) The ab-pane contains large square cavities formed by quadruple cross-linking of nanoballs. (b.) Cross-linking as seen along a- and
b-axes, note that the ligands adopt a syn-conformation. (c.) Cross-linking as seen along the c-axis. Note here that the ligands adopt an
anti-conformation.
1412 | Chem. Soc. Rev., 2009, 38, 14001417 This journal is c The Royal Society of Chemistry 2009
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1,3-bdc moieties. Nevertheless, the resulting surface area is
such that this compound reversibly stores the highest weight
percent of H
2
at 1 bar and 77 K thus far observed in a MOM.
3.3.1.4 rht nets. Within the past year, two research groups
have independently reported topologically related examples of
extended MOMs for which nanoballs were used as SBBs. The
targeted network, the (3,24)-connected rht net, is a topology
only recently addressed by Delgado-Friedrichs and
OKeee
199
as the only edge transitive binodal net involving
triangles and rhombicuboctahedra (which shares the same
edge skeleton as the small rhombihexahedron). Eddaoudi
and Zaworotko
200
presented the rst metalorganic example
of an rht-like network. The authors realized that the nanoball
SBB could in principle serve as a 24-connected node if each of
24 vertices could be linked through trigonal 3-connected units,
thereby generating an rht-like network from rst principles
([14], Table 1). Judicious chemical modication at the
5-position of bdc was performed to facilitate formation of a
trigonal SBU through coordination chemistry. The authors
synthesized 5-tetrazolylisophthalic acid (H
3
TZI) (Fig. 26)
which, when reacted with Cu(NO
3
)
2
2.5H
2
O in DMFEtOH
under solvothermal conditions, generated a framework
characterized as [Cu
6
O(TZI)
3
(H
2
O)
9
(NO
3
)]
n
(H
2
O)
15
in which
each nanoball is connected to a trigonal Cu
3
O(N
4
CR)
3
unit
through each tetrazolate (N
4
CR) moiety (Fig. 27).
The authors noted that this compound could also be
described as a novel 3-periodic (3,3,4)-connected ternary
net
201
which is based upon three geometrically dierent SBUs.
The framework contains three distinct open cages, the largest
of which contains a 2 nm diameter cavity when van der Waals
radii are considered. This cage is bordered by 24 square
paddlewheel SBUs and 8 trigonal SBUs such that it is
Fig. 26 5-Tetrazolylisophthalic acid.
Fig. 27 (Top) A single metalorganic nanoball shown with 24 Cu
2+
tetrazole trimers (red triangle in scheme) around the periphery.
(Bottom) A single trimer connected to three nanoball SBBs. When
coupled these components highlight the (3,24)-connected nature of this
rht-like network.
Fig. 28 Illustration of the rht network from a tile perspective. The
central tile represents the largest cage formed from six surrounding
metalorganic nanoballs and the Cu
3
O(N
4
CR)
3
trimers (red triangles)
linking them.
Fig. 29 C
3
-symmetric ligand: 5,5
0
,5
00
-[1,3,5-benzenetriyltris(carbonyl-
imino)]tris-1,3-benzene dicarboxylic acid.
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surrounded by 6 nanoballs (Fig. 28) and 8 tetrahedral-like
cages (which are deleted in Fig. 28 for clarity). The authors
estimate that the total solvent-accessible volume for this
MOM is B75% and they demonstrated that this material
possesses permanent porosity.
Lah and co-workers synthesized another example of an
extended MOM with rht-like topology
202
by utilizing covalent
bonding. They synthesized a C
3
-symmetric facial ligand,
5,5
0
,5
00
-[1,3,5-benzenetriyltris(carbonylimino)]tris-1,3-benzene
dicarboxylic acid (Fig. 29), which can be regarded as three
1,3-bdc moieties linked through a trigonal organic unit. This
version of the rht net was synthesized in a one-pot reaction
involving Zn(NO
3
)
2
6H
2
O, the C
3
-symmetric ligand described
above, and dimethylacetamide. The authors noted the
presence of large tetrahedral cavities interconnected with large
pores and a solvent-accessible free volume of B71%.
However, they did not explicitly identify the network as rht-like.
A third example of an extended MOM with rht-like
topology has been described by Schro der and co-workers.
203
They exploited a rigid C
3
-symmetric hexacarboxylate ligand,
1,3,5-tris(3
0
,5
0
-dicarboxy[1,1
0
-biphenyl]-4-yl)benzene, which is
in eect three 1,3-bdc units bridged by a trigonal organic
moiety. Combining this ligand with Cu(NO
3
)
2
3H
2
O in a 5 : 1
N,N
0
-dimethylformamide : dimethyl sulfoxide solution (in the
presence of a small quantity of H
2
O) in a solvothermal
reaction resulted in blue octahedral-shaped single crystals in
high yield ([16], Table 1). The authors noted the large
cages and pores generated in their structure and reported a
solvent-accessible free volume of B75% consistent with earlier
rht-like MOFs. While the H
2
uptake at 1 bar and 77 K is
comparable to that of the rht-MOF reported by Eddaoudi and
Zaworotko [14] (2.3% vs. 2.4% total H
2
uptake), at higher
pressures Schro ders compound demonstrates a maximum
excess H
2
uptake of 7.07% between 35 and 40 bar (total
uptake of 10.0 wt% at 77 bar) making it comparable to the
highest reported uptakes of H
2
for any MOF at 77 K.
4. Concluding remarks and future prospects
It is an understatement to assert that the eld of MOMs has
undergone explosive growth in the past 10 years. However,
MOMs are only beginning to exhibit their promise in terms of
design and functional properties. As such, new methods
and strategies for their design and synthesis are needed to
complement those that have been successful in the past. We
believe that the design strategy we address herein, the
exploitation of MOPs as SBBs for the generation of extended
MOMs, oers several attractive features that collectively make
a compelling case for further pursuit of such structures:
They oer compositional diversity since they are inherently
modular in their nature. Indeed, the SBBs and MOMs
presented herein can all be regarded as prototypal, suggesting
the promise of ne-tuning or customizing the cavities and bulk
properties through judicious choice of metals, counterions or
ligands.
High symmetry brings with it an ability to invoke crystal
engineering since SBBs of rare or unprecedented coordination
number oer improved or even exquisite control over network
topology.
Such SBBs also oer structural diversity through the
ability to control connectivity between SBBs, thereby generating
multiple topologies from the same SBB (e.g. nanoballs can be
connected via linear or triangular connectors).
The inherently facile and self-correcting nature of
synthetic approaches that rely upon self-assembly means that
one-pot processes from simple starting materials are the norm
rather than the exception.
This critical review is intended to act as a guide for those
interested in pursuing the SBB strategy for generation of
extended MOMs and to serve as validation that materials
designed through this strategy are not only of general interest
due to their inherent beauty and form, but that they are likely
to be of practical importance because of their scale and ready
accessibility. Indeed, the SBB strategy begs the following
question: what are the realistic limits of scale for MOMs in
terms of cavity size, pore size, and surface area?
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