This is an open access article published under a Creative Commons Attribution (CC-BY)

License, which permits unrestricted use, distribution and reproduction in any medium,
provided the author and source are cited.

Outlook

[Link]

Porous Molecular Solids and Liquids

Andrew I. Cooper*
Department of Chemistry and Materials Innovation Factory, Leverhulme Centre for Functional Materials Design, University of
Liverpool, 51 Oxford Street, Liverpool, L7 3NY, United Kingdom

ABSTRACT: Until recently, porous molecular solids were isolated

curiosities with properties that were eclipsed by porous frameworks,
such as metal−organic frameworks. Now molecules have emerged as a
functional materials platform that can have high levels of porosity,
good chemical stability, and, uniquely, solution processability. The lack
of intermolecular bonding in these materials has also led to new,
counterintuitive states of matter, such as porous liquids. Our ability to
design these materials has improved significantly due to advances in
computational prediction methods.

all of which are connected by intermolecular bonds. The field

P orous molecular materials have been featured in previous
reviews,1−16 some of which have also given histories of this
field,5,15 which dates to work in the 1970s by Barrer and
of extended porous frameworks and networks is burgeoning:
the area of porous MOFs alone is vast. Why, then, do we need
Shanson on organic zeolites.17−24 This Outlook will not repeat another flavor of porous material? We believe that porous
those reviews but will focus instead on the rapidly emerging molecular materials are complementary to more established
opportunities in this area. porous solids because of their distinguishing features, which

■ TERMINOLOGY
For the purposes of this review, “porous molecular materials” or
include the following.
Noncovalent Synthesis. MOFs are synthesized directly as
insoluble solids by metal−organic bond formation; COFs are
“porous molecules” are porous solids or liquids where the generated using reversible covalent bonds. By contrast, porous
molecular subunits are not connected by strong intermolecu- molecular crystals are produced by crystallization, in which no
lar bonds, such as coordination bonds or covalent bonds. new bonds are formed. It is hence relatively easy to grow large,
We further define “molecule” as a discrete molecule with a high-quality porous molecular crystalsfor example by slow
specific molar mass, as opposed to a polymer, although we do solvent evaporation (Figure 1a)29although in some cases,
touch briefly on polymers of intrinsic microporosity (PIMs),
which are in a sense also “porous molecular materials”. “Porous
organic cages” (POCs), “hydrogen-bonded organic frame-
works” (HOFs), and “supramolecular organic frameworks”
(SOFs) are hence all subclasses of porous molecular materials.
“Extrinsic” and “intrinsic” porosity, respectively, refer to pores
that are located between molecules or within molecules,
typically inside a cage. For example, “organic molecules of
intrinsic microporosity” (OMIMs) are molecular solids that are
extrinsically porous because the rigid molecules pack badly;
they do not have intrinsic porosity built into the molecule, as
in a porous organic cage. “Extended frameworks” refers to
crystalline solids comprising strong intermolecular coordination
or covalent bonds, such as metal−organic frameworks (MOFs)
or covalent organic frameworks (COFs), unless specified; Figure 1. Porous molecular materials can be produced as (a) crystalline
solids,64 (b) amorphous solids,36,42 or (c) liquids.48 For scale, the coin
for example, where discussing “amorphous MOFs”. “Porous
diameter in panel a is 22.5 mm. The amorphous thin film in panel b is
polymer networks” are extended covalent networks that, unlike made from a scrambled cage mixture, composition denoted by the
COFs, are amorphous rather than crystalline; these have chromatogram. Panel c, lower, shows xenon gas being displaced from a
extended bonding throughout the network and are hence porous liquid by chloroform. In all cases, cycloimine cages are depicted,
insoluble, unlike PIMs. formed from the [4 + 6] condensation of 1,3,5-triformylbenzene with

■
various 1,2-substituted vicinal diamines.
WHY POROUS MOLECULES?
Porous molecular materials are composed of discrete molecules, Received: April 7, 2017
unlike MOFs,25,26 COFs,16,27 and porous polymer networks,16,28 Published: May 18, 2017

© 2017 American Chemical Society 544 DOI: 10.1021/acscentsci.7b00146

ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

specific desolvation protocols are required to retain order and Structural Flexibility. Since we first surveyed the field of
porosity.30,31 By comparison, erroneous side reactions may porous organic molecules,2 the area of flexible MOFs has
become locked into MOFs and COFs, even when the advanced significantly.50−52 Nevertheless, our original com-
chemistry is reversible, although this can also be viewed as a ments2 still hold: molecular crystals are not interconnected by
tool to engineer properties.32 Defects can certainly be prevalent strong covalent or coordination bonds, and they can undergo
in porous polymer networks formed by irreversible routes.33 large rearrangements in the solid state. This has led to
The ability to grow high-quality porous molecular crystals is a molecular crystals with “on/off” porosity switching behavior
potential advantage in applications that require long-range (Figure 3)53 and, recently, macrocyclic pillar[n]arenes that
order. It also aids characterization: for example, most of our show extremely high selectivity for styrene over ethylbenzene
porous organic cage structures were solved by single-crystal via a guest-induced restructuring process.54
X-ray diffraction, whereas there are very few examples of single-
crystalline COFs.34,35
Solubility. Unlike extended frameworks, many porous
molecules are soluble in organic solvents. They can be solution
processed into a variety of forms, such as thin films and
membranes. This applies to molecular cages (Figure 1b),36
polymers of intrinsic microporosity (PIMs),21,37 and organic−
organic mixed-matrix membrane (MMM) composites,38,39
where a crystalline porous molecular filler reduces membrane
aging.
Amorphous Porous Solids and Porous Liquids. Porous
molecules do not have to be crystalline solids. PIMs, a large and Figure 3. On/off porosity switching in a porous organic cage crystal.53
Guest 1 transforms the molecule into a porous polymorph; guest 2
growing class of materials, are amorphous.21,37,40 Like- transforms it into a nonporous polymorph. This suggests a potential
wise, smaller molecules can form amorphous porous phases guest trapping mechanism for hazardous or valuable molecules.
(Figure 1b),41−44 and certain porous organic cages can be The cage molecule is a [4 + 6] cycloimine cage with flexible
processed deliberately into either amorphous or crystalline 1,2-diaminoethane vertices.
forms: the amorphous forms retain the porosity imparted by
the cage, but have different physical properties (Figure 2).29 Stability. Intuitively, porous molecular solids might be
expected to be less stable than extended MOFs and COFs. This
is not always the case. For one thing, it is not essential to use
reversible, dynamic chemistry to make crystalline porous
molecules. Rigid molecules that pack badly to create so-called
“extrinsic” porosity date back to Barrer’s early studies on
Dianin’s compound.17,19,30 Likewise, macrocyclic calixarenes22
are not prone to the chemical instability that can be associated
with highly reversible MOF and COF chemistries. There are
fewer examples of intrinsically porous cage molecules formed
using irreversible coupling routes, but the work of Doonan on
alkyne-linked cages points the way there, too.55,56 Chemical
stability and crystal stability are not the same thing, but they are
frequently interlinked, and certain chemically stable porous
molecular crystals show stabilities that exceed those of most
MOFs and COFs. For example, we reported a highly crystalline
Figure 2. Some amorphous molecular cage solids can be more porous [4 + 6] porous organic aminal cage with good chemical and
than their crystalline counterparts;29 typically, the reverse is true for crystal stability in water for 12 days at pH values ranging from
MOFs. The molecule shown is a tetrahedral [4 + 6] cycloimine cage 1.7 to 12.3 (Figure 4).57 Likewise, Banerjee has shown that
with (R,R)-1,2-cyclohexanediamine vertices, packed (a) as a crystalline
porous solid and (b) as an amorphous porous solid.
porous organic cages can be stable under both acidic and basic
conditions because of keto−enol tautomerism.58 Few MOFs or
COFs are stable over such broad pH ranges; indeed, most
Amorphous MOFs45 are a related, emerging class of material, zeolites are unstable under either acidic or basic conditions.
but these are typically formed by amorphization of a parent To our knowledge, these cage molecules57,58 are among the
crystalline framework, for example by ball milling. Amorphous most chemically resistant crystalline microporous solids known,
porous molecular solids can be prepared directly by using although they are currently isolated examples. The dream of
processing tricks, such as rapid solvent removal,46 or by molecular organic zeolites17 lives on.
making molecules unsymmetrical so that they cannot crys-
tallize.42 Amorphous MOFs are typically less porous than their
crystalline porous counterparts, whereas some cages, such as
■ POROUS MOLECULAR CRYSTALS
Notwithstanding the differences summarized above, there are
CC3, a [4 + 6] cycloimine cage, are substantially more porous also many similarities between porous molecular crystals and
as amorphous solids (Figure 2).29 The most radical extension extended MOFs and COFs. Extended frameworks are syntheti-
of this amorphization concept is the idea of porous molecular cally diverse because an almost unlimited array of organic
liquids (Figure 1c); these can be accessed by designing porous linkers is conceivable. It is also possible to carry out post-
molecules that melt47 or that are highly soluble in size-excluded synthetic modifications on extended porous frameworks59
solvents.48,49 and to mix different linkers,60 further increasing this diversity.
545 DOI: 10.1021/acscentsci.7b00146
ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

corresponding values for COF-103 were 4210 m2 g−1 and

0.38 g cm−3.66 This gulf between porous molecular crystals and
extended frameworks has since narrowed.67 Mastalerz has
led the way here, producing an intrinsically porous organic
boronate ester cage (3758 m2 g−1/desolvated density not
reported)31 and an extrinsically porous hydrogen-bonded
benzimidazolone framework (2796 m2 g−1/0.755 g cm−3),30
both with porosity levels that are remarkable for molecular
solids. The least dense desolvated molecular solid to date has a
density of just 0.41 g cm−3.68 For most practical purposes, then,
porous molecular crystals can be considered somewhat
competitive with MOFs and COF in terms of available
porosity. A caution, though, is that physical and chemical
stability is a likely concern for any crystalline solid with a very
low density (e.g., <0.5 g cm−3), irrespective of material subclass.
As commented before,69 robust activated carbons have been
commercially available since the 1990s with surface areas of
more than 3000 m2 g−1. Functional added value will be needed
to propel porous molecular crystals, and other porous
frameworks, toward applications. Some of the more interesting
targets might be small-pore, low surface area solids that can
perform challenging separations.54,70,71 Taking that argument
further, “zero-dimensional”72 porous molecular crystals may be
interesting for gas storage and release.
Extrinsically porous molecular crystals17,19,21,22 predate the
first intrinsically porous organic cages,64,73 but until recently,
Figure 4. Porous molecular crystals can have good chemical stability. the levels of porosity in extrinsically porous crystals were
This cage crystal is stable over a pH range of 1.7−12.3, and neither the modest, and their potential applications largely hinted at.
X-ray diffraction pattern (a) nor the nitrogen sorption isotherm (b) is That picture is changing; a range of porous hydrogen-bonded
affected by acid or base treatment.57 Inset shows predicted (red) and organic frameworks (HOFs)74also referred to as supra-
observed (blue) conformation for the cage. The cage molecule is made molecular organic frameworks (SOFs)75has now been
stable by reduction of the imine functionalities and conversion to an reported.30,68,74−93 The most porous of these so far are
aminal. The lower panel shows the stability range for the cage, mapped Mastalerz’s triptycene benzimidazolone and analogues,30,68 but
onto the pH scale as depicted by universal indicator colors. multiple properties have been studied in addition to surface
area, such as fullerene capture,76 uranium capture,86 fluoro-
The synthetic space for porous molecular materials has the
carbon capture,94 ion absorption,89 proton conduction,78
potential to be equally large. As for extended frameworks,
thermoelasticity,79 sensing,81,84,87 enantioseparations,91 CO2
multiple building blocks can be combined within a single
separation,78,80,82,85,90,95 and hydrocarbon separation.68,74,92
porous solid42,61,62 (or porous liquid).48,49 Also, like MOFs and
This is a rapidly developing area, and solution processability
COFs, porous molecules can be postfunctionalized to vary the
physical properties.57,63 is a potential advantage for HOFs and SOFs, too. Based on
these developments, intrinsically and extrinsically porous
molecules look set to be equally valid strategies for the future.
However, since porous molecular The initial focus for porous molecular crystals was on gas
crystals and porous extended adsorption and molecular separations, although recent studies
frameworks can now be thought suggest that they might also be relevant in “second generation”
of somewhat interchangeably, framework applications, such as proton conductivity.78,96 An
obvious exception here would be conjugated COFs,97 where
the most profitable areas for there are as yet no molecular analogues; a worthy future target.
porous molecular materials in the For some applications, such as the separation of krypton and
future might exploit one or more xenon, molecular crystals were demonstrated to have better
of the differentiating features selectivity than extended frameworks,70 at least transiently.98
However, since porous molecular crystals and porous extended
listed above. frameworks can now be thought of somewhat interchangeably,
the most profitable areas for porous molecular materials in the
One difference between porous molecular crystals and extended future might exploit one or more of the differentiating features
porous frameworks is the density and surface area range that can listed above. There are several underexplored areas. For example,
be accessed. When the first porous organic cages were reported in hydrolytically stable “molecular molecular sieves”57,99 could have
2009, the most porous molecules had a Brunauer−Emmett− applications in water purification100 and, potentially, desalination,
Teller (BET) surface area of around 600 m2 g−1, corresponding to especially if they could be solution-cast as crystalline thin films
a crystal density of 0.973 g cm−3.64 By comparison, the most with adequate permeance. Likewise, there is just one report so
porous MOF at that time, UMCM-2,65 had a surface area of far of solution-cast organic−organic MMM composites, which
5200 m2 g−1 and a crystal density of 0.401 g cm−3; the involved a polymer of intrinsic microporosity (PIM-1) and an
546 DOI: 10.1021/acscentsci.7b00146
ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

organic imine cage (CC3),38 and this is an unexplored play- More generally, porous liquids
ground for the future.39,101

■
might stimulate new thinking in
INTRINSICALLY POROUS FRAMEWORK LINKERS almost any area that uses liquid
Porous molecules can also be used as linkers in extended solvents; for example, one could
frameworks to obtain additional functionality. As yet, there are envisage porous extraction
few reports of “cage MOFs”102 or “cage polymers”103 (and no media, porous cleaning fluids, or
reports of crystalline “cage COFs”), but in principle this should porous electrolytes.
be a fertile area, noting that MOFs were already synthesized
from macrocycles, such as cyclodextrins.104 To give one
example, MOFs can be prepared from amine cages, where either guest molecules, such as pyrene, were blended into
the amines act as metal coordination ligands and the cage linker scrambled porous imine cage materials or, alternatively, the
provides a (limited) degree of intrinsic porosity.102 cages were blended into otherwise nonporous linear polymers.
It ought to be possible to create a wide range of intrinsically There are multiple opportunities here. For example, a cheap
porous cage linkers for MOFs, particularly as we extend the commercial polymer, such as polystyrene, might be rendered
range of cage topologies that are available (e.g., 1-D tubular porousor at least permeableby simply blending it with
cages105). To achieve this, it might be necessary to develop molecular pores. A further opportunity might exist in catalysis,
porous molecules with extra peripheral functionality106,107 to where a molecular catalyst is physically blended with molecular
allow for metal chelation or for COF formation. It might even pores to create an amorphous microporous composite. As a
be possible to create mechanically bonded cage linkers for proof of concept, we showed that molecular pyrene could be
MOFs or for COFs.108−110 uniformly distributed throughout an amorphous cage matrix at

■
loadings of up to around 10 wt %, without losing microporosity
(Figure 6).116 Metal catalysts, or organocatalysts, could be
AMORPHOUS POROUS MOLECULAR SOLIDS
There are fewer well-characterized examples of amorphous
porous molecular solids in comparison with porous molecular
crystals, at least for smaller molecules; PIMs is a more
developed area.21,37,40 One of the first detailed studies on
porous small-molecule amorphous solids was carried out by
Atwood and co-workers.41 Subsequently, much more porous
amorphous molecular solids were reported,29 including rigid
organic molecules of intrinsic microporosity (OMIMs)44,111
and “scrambled” organic imine cages that are purposefully
desymmetrized such that they cannot crystallize.42 Amorphous
porous molecular solids present interesting opportunities: like
PIMs, they are solution processable and amorphous, but unlike
PIMs, they can have prefabricated cavities and window sizes
with precisely defined size and geometry, although these are
typically interconnected by less well-defined extrinsic pores
(Figure 2b).43 These molecular solids can be cast, like PIMs,
using standard procedures such as spin-coating to give uniform
conformal thin films (Figure 1b).36 The amorphous imine cage
films tested in our preliminary studies had, in fact, worse aging
characteristics than PIMs,36 but if that problem could be solved, Figure 5. Porous molecular crystals can have remarkably high surface
then similar systems might be useful for gas separations. areas. Both intrinsic porosity (pores within the molecule)31 (a) and
For example, the inherent size,70,112 shape,71,112−114 or extrinsic porosity (pores between molecules)30 (b) are valid routes for
chiral70,113 selectivity of porous organic cages might be exploited doing this.
in thin, amorphous layers supported on a more permeable
polymer support, or within a separation column.71,113 blended into similar materials, which can also be chiral.70 This
A different mechanism for molecular separations is guest- would be a different paradigm from more conventional catalyst
induced restructuring, related to adductive or reactive crystal- supports, such as MOFs,117 although at this stage the benefits
lization processes,115 which can be applied to both crystalline and drawbacks are unclear; clearly, solubility of the cage
and amorphous molecular phases alike.54 Here, separation support itself might preclude some applications.
occurs because of selective conversion to a specific crystalline
guest inclusion compound; that is, the host molecule chooses a
specific guest, and is restructured by it. Such processes can be
■ POROUS MOLECULAR LIQUIDS
Porous liquids are liquids with permanent rather than transient
exquisitely selective,54 but slow uptake kinetics and energy pores. The concept and technical challenges were first discussed
requirements for guest release are questions to address in terms by James in 2007.118 It proved challenging, however, to
of practical molecular separations. Again, the solution process- translate these ideas into reality. The “dam”119 for porous
ability of these materialsperhaps onto or into a support liquids has now burst; since 2012, six papers have been
material46might offer a way forward. published that describe these materials and their proper-
Another untapped area is amorphous, porous molecular ties,47−49,120−122 and five of these studies were based on
composites. There is just one report of this so far,116 in which shape-persistent [4 + 6] porous organic imine cages.47−49,120,122
547 DOI: 10.1021/acscentsci.7b00146
ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

accelerate the rate of reactions involving gases (e.g., H2, O2,

ethylene, etc.), perhaps allowing reactions to be carried out at
lower gas pressures. More generally, porous liquids might
stimulate new thinking in almost any area that uses liquid
solvents; for example, one could envisage porous extraction
media, porous cleaning fluids, or porous electrolytes.
This discussion has focused on porous molecular liquids.
Of equal interest in the future might be porous liquids, or
“fluidized porous solids”, that comprise a colloidal porous
solid dispersed at a high loading in a suitable carrier fluid.121
In principle, this carrier fluid could itself have molecular,
prefabricated porosity,47−49 for example to increase mass trans-
port or to improve selectivity.

■
Figure 6. Molecular organic pores can be blended with guest
molecules to make porous amorphous composites. Here, a scrambled
DESIGNING POROUS MOLECULAR MATERIALS
porous imine cage (see Figure 1b) is blended with pyrene to make
fluorescence composite powders (a, b).116 The composites retain Exciting as they are, porous molecular materials are quite
microporosity up to around 10 wt % pyrene loading (c). This suggests challenging to design. Indeed, the rarity of porosity in
applications such as catalysis, where a metal catalyst or organocatalyst crystalline organic materials is illustrated by a recent study,125
is blended with molecular pores, rather than being attached to a
preformed porous catalyst support.
which found only a handful of porous molecular crystals from a
sampling of more than 150,000 reported structures. Reticular
The fundamental distinction between a porous liquid and a synthesis126 is a powerful tool for designing crystalline porous
porous solid is fluidity, which has various potential process extended frameworks, but the (older) concept of crystal
benefits; for example, liquids can be pumped around in a engineering127 for porous molecular crystals has proved some-
continuous system, which could facilitate guest loading and what less generalizable. This is mostly because intermolecular
unloading steps. This assumes, of course, that the porous liquid interactions in molecular crystals are, in general, weaker and
viscosity is low enough to allow this. It has already been shown less directional than metal−organic bonding in MOFs or
that porous liquids can have gas sorption capacities that are covalent bonding in COFs.27 There are hence few isoreticular
atypically high for liquids. In principle, other properties of strategies for porous molecular solids. Heterochiral window
porous solids should translate into porous liquids, such as guest interactions between cages have proved strong enough to serve
selectivity. as a platform for reliable crystal engineering,46,61,62,105,128−130
although in some cases, this interaction needs additional
Ultimately, though, molecular reinforcement by the inclusion of a shape-specific “directing
structure and solid-state structure solvent”,128 and it does require the use of homochiral feedstocks.
One of the most attractive design strategies for porosity
cannot be disconnected. generation in molecular solids is to prefabricate the pores in the
molecule itself, not least because molecular porosity and shape-
There are several interesting research targets for porous persistence can be predicted, a priori, for candidate cage
liquids. First, these materials should be benchmarked against building blocks.131−134 For example, the [4 + 6] organic imine
existing high free-volume liquids, such as ionic liquids and cage, CC3, is porous in the crystalline state64 by virtue of its
polyethers (e.g., Selexol),123 though it may be noted that those molecular structure: few crystalline packings for CC3 are
solvents have been explored more for acidic gases, and that nonporous, even hypothetical ones. CC3 is also porousmore
porous liquids are applicable to neutral gases, such as light porous, in factas an amorphous solid (Figure 2b).29
hydrocarbons and xenon.48,49 A second challenge is to create This strategy of molecular design can also succeed for porous
porous liquids with lower volatility or, ideally, zero volatility liquids, where it is possible to pair shape-persistent porous
(e.g., a porous ionic liquid); in this respect, the crown ether or cages with bulky solvents that are size-excluded from the cage
perchlorinated solvents used in our first systems48,49 are not windows.48,49 Ultimately, though, molecular structure and
ideal. A third area to explore is guest adsorption and release solid-state structure cannot be disconnected. To give one
kinetics: low- or zero-volatility porous liquids should facilitate example, crystalline CC3 shows perfect selectivity for C9
pressure-swing or temperature-swing adsorption/desorption
aromatic hydrocarbon separation whereas the amorphous form
cycles. We also showed recently that less standard stimuli,
of the same molecule does not.71 The need to understand the
such as ultrasonication,49 can promote gas release from porous
liquids, although it is unclear that this would be scalable or cost- crystal packing (or amorphous packing) is even more apparent
effective in real processes. for extrinsically porous molecules, where the likely physical
Gas adsorption and separation are not the only possible properties may not be obvious at all from the building blocks in
applications for these new materials. Porous liquids might have isolation.17,19,30 There are two solutions here: the develop-
unique properties for homogeneous catalysis: for example, they ment of robust intermolecular synthons or “tectons” that will
could provide reaction selectivity by confinement124 or by facilitate the intuitive design of porous molecular frame-
chiral induction, though we showed recently that porous chi- works18,30,105,127,128 or the a priori prediction of structure
ral cage liquids did not exhibit chiral selectivity,49 unlike a from the molecular formula, irrespective of the intermolecular
crystalline homochiral porous solid formed from a similar cage forces.135 Some of the most powerful strategies might lie at the
molecule.70 It is also possible that porous liquids could confluence of these two ideas.
548 DOI: 10.1021/acscentsci.7b00146
ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

Figure 7. Crystal engineering for porous molecular solids is challenging because the intermolecular interactions are typically weaker and less
directional than for extended frameworks, such as MOFs and COFs. Energy−structure−function (ESF) maps can reveal the function−energy
landscape for a candidate molecular building block.68 Here, a benzimidazolone molecule (cf., Figure 5b) was shown to have at least four stable porous
polymorphs (T2-α−T2-δ; red = predicted structures; blue = experimental crystal structures). T2-γ was predicted to have the most competitive
methane delivery capacity (159 v STP/v), as confirmed by experiment.

■ ENERGY−STRUCTURE−FUNCTION MAPS
Crystal engineering has proved successful for porous molecular
porous polymorphs with predicted densities in the broad range
0.4−1.25 g cm−3 and predicted surface areas ranging from 442
to 3230 m2 g−1.68 All four of these structures were located on
solids, but it works best within specific subclasses of materials,
the low-energy boundary, or “leading edge” of the calculated
such as chiral organic cages.46,61,62,105,128 There is no synthon
energy−structure landscape (Figure 7). By calculating physical
or tecton for porous molecular solids that is as versatile as, say,
properties for each structure on a predicted energy−structure
metal carboxylate bonding in isoreticular MOFs,136 let alone a
landscape, we produced energy−structure−function (ESF)
“magic bullet” for the reliable construction of porous molecular
maps.68 These color-coded maps can suggest, at a glance,
frameworks. In collaboration with colleagues at the University
which molecule in a candidate set might be most appropriate
of Southampton, we have explored strategies for designing
for a given application, such as methane storage68 (Figure 7) or,
porous molecular solids using crystal structure prediction
by extension, any other physical property that can be calculated
(CSP).62,68,105,129 This approach involves the application of
from structure. The use of ESF maps should extend beyond
space group symmetry followed by energy minimization and
porous solids, and is in principle applicable to any physical
lattice energy calculation,137 and it assumes no favored
property that can be calculated from crystal structure.

■
topology or specific intermolecular tectonic interaction.
In principle, therefore, CSP is generalizable, although there
still are difficult technical challenges, such as the computational OUTLOOK
expense of dealing with large or flexible molecules. We first The area of porous molecular materials has matured
showed that CSP can be used to predict the structures of significantly in the past few years through the combined efforts
porous organic cages.62 It was shown that the observed of several research groups worldwide. The field has evolved
tendency for porous, chiral cage molecules such as CC3 to from a set of mostly isolated examples to include series of
crystallize in a window-to-window fashion64 was manifested in a related materials that were designed in a broadly isoreticular
large calculated lattice energy gap between the global minimum fashion.46,61,62,105,128,129 Very recently, Diercks and Yaghi
predicted structure and the bulk of the energy−structure surveyed the area of COFs139 and stated that, for crystalline
landscape.62 For other, less directional cage molecules, such as COFs, “covalent bonds create robustness and directionality
the polymorphic, racemic cage CC1,53 the calculated lattice (necessary to control the spatial orientation of the building
energy differences between structures were much smaller.64 blocks)”. In this author’s view, the use of intermolecular
Hence, these CSP methods provide us with a means to covalent bonds is not always required for directionality in
distinguish between molecules with deep-lying, unique global crystalline organic solids,62,105 nor does it necessarily produce
minimathat is, robust tectonsand molecules that are more greater chemical robustness.57,58,140 Certainly, the less predict-
likely to exhibit polymorphism. Based on such analyses, CC3 able nature of noncovalent supramolecular assembly has often
would be predicted from its energy−structure landscape to be a thwarted the purposeful design of molecular crystals, but that
robust tecton,62 whereas CC1 would not.129 More recently, the could be set to change.68,141 This raises an interesting question:
CSP approach was extended to extrinsically porous mole- if MOF, COF, porous polymer, and porous molecular solid
cules,68,138 such as the hydrogen-bonding frameworks devel- syntheses were all perfectly predictable, then which class of
oped by Mastalerz.30 We showed that the energy−structure porous solid would one choose? The humorous answer is zeolites.
landscapes for such molecules can be complex: for example, a Less frivolously, attention would undoubtedly turn to function,
trigonal benzimidazolone was found to have at least four stable cost, and sustainability.11 In that regard, solution-processable,
549 DOI: 10.1021/acscentsci.7b00146
ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

robust porous molecular crystals might fill a unique space in the (19) Sozzani, P.; Comotti, A.; Simonutti, R.; Meersmann, T.; Logan,
wide roster of applications for porous materials. J. W.; Pines, A. A Porous crystalline molecular solid explored by

■
hyperpolarized xenon. Angew. Chem., Int. Ed. 2000, 39, 2695−2699.
(20) Shimizu, L. S.; Hughes, A. D.; Smith, M. D.; Davis, M. J.; Zhang,
AUTHOR INFORMATION B. P.; zur Loye, H. C.; Shimizu, K. D. Self-assembled nanotubes that
Corresponding Author reversibly bind acetic acid guests. J. Am. Chem. Soc. 2003, 125, 14972−
*E-mail: aicooper@[Link]. 14973.
(21) Budd, P. M.; Ghanem, B. S.; Makhseed, S.; McKeown, N. B.;
ORCID Msayib, K. J.; Tattershall, C. E. Polymers of intrinsic microporosity
Andrew I. Cooper: 0000-0003-0201-1021 (PIMs): robust, solution-processable, organic nanoporous materials.
Chem. Commun. 2004, 230−231.
Notes (22) Atwood, J. L.; Barbour, L. J.; Jerga, A. A new type of material for
The author declares no competing financial interest. the recovery of hydrogen from gas mixtures. Angew. Chem., Int. Ed.

■
2004, 43, 2948−2950.
ACKNOWLEDGMENTS (23) Tranchemontagne, D. J. L.; Ni, Z.; O’Keeffe, M.; Yaghi, O. M.
Reticular chemistry of metal-organic polyhedra. Angew. Chem., Int. Ed.
The author acknowledges support from the Engineering and 2008, 47, 5136−5147.
Physical Sciences Research Council (EP/N004884/1), the (24) Msayib, K. J.; Book, D.; Budd, P. M.; Chaukura, N.; Harris, K.
European Research Council under the European Union’s D. M.; Helliwell, M.; Tedds, S.; Walton, A.; Warren, J. E.; Xu, M. C.;
Seventh Framework Programme (FP/2007-2013) through McKeown, N. B. Nitrogen and Hydrogen Adsorption by an Organic
Grant Agreement No. 321156 (ERC-AG-PE5-ROBOT), and Microporous Crystal. Angew. Chem., Int. Ed. 2009, 48, 3273−3277.
the Leverhulme Trust for Funding. (25) Kondo, M.; Yoshitomi, T.; Matsuzaka, H.; Kitagawa, S.; Seki, K.

■
Three-dimensional framework with channeling cavities for small
molecules: {[M2(4, 4′-bpy)3(NO3)4]·xH2O}n (M - Co, Ni, Zn).
REFERENCES Angew. Chem., Int. Ed. Engl. 1997, 36, 1725−1727.
(1) Barbour, L. J. Crystal porosity and the burden of proof. Chem. (26) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The
Commun. 2006, 1163−1168. chemistry and applications of metal-organic frameworks. Science 2013,
(2) Holst, J. R.; Trewin, A.; Cooper, A. I. Porous organic molecules. 341, 1230444-1−1230444-12.
Nat. Chem. 2010, 2, 915−920. (27) Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O’Keeffe, M.; Matzger,
(3) McKeown, N. B. Nanoporous molecular crystals. J. Mater. Chem. A. J.; Yaghi, O. M. Porous, crystalline, covalent organic frameworks.
2010, 20, 10588−10597. Science 2005, 310, 1166−1170.
(4) Tian, J.; Thallapally, P. K.; McGrail, B. P. Porous organic (28) Dawson, R.; Cooper, A. I.; Adams, D. J. Nanoporous organic
molecular materials. CrystEngComm 2012, 14, 1909−1919. polymer networks. Prog. Polym. Sci. 2012, 37, 530−563.
(5) Mastalerz, M. Permanent porous materials from discrete organic (29) Hasell, T.; Chong, S. Y.; Jelfs, K. E.; Adams, D. J.; Cooper, A. I.
molecules-towards ultra-high surface areas. Chem. - Eur. J. 2012, 18, Porous organic cage nanocrystals by solution mixing. J. Am. Chem. Soc.
10082−10091. 2012, 134, 588−598.
(6) Ono, K. Porous organic cage crystals. Yuki Gosei Kagaku (30) Mastalerz, M.; Oppel, I. M. Rational construction of an extrinsic
Kyokaishi 2012, 70, 653−654. porous molecular crystal with an extraordinary high specific surface
(7) Jelfs, K. E.; Cooper, A. I. Molecular simulations to understand area. Angew. Chem., Int. Ed. 2012, 51, 5252−5255.
and to design porous organic molecules. Curr. Opin. Solid State Mater. (31) Zhang, G.; Presly, O.; White, F.; Oppel, I. M.; Mastalerz, M. A
Sci. 2013, 17, 19−30. permanent mesoporous organic cage with an exceptionally high
(8) Zhang, G.; Mastalerz, M. Organic cage compounds - from shape- surface area. Angew. Chem., Int. Ed. 2014, 53, 1516−1520.
persistency to function. Chem. Soc. Rev. 2014, 43, 1934−1947. (32) Fang, Z. L.; Bueken, B.; De Vos, D. E.; Fischer, R. A. Defect-
(9) Jin, Y. H.; Wang, Q.; Taynton, P.; Zhang, W. Dynamic covalent engineered metal-organic frameworks. Angew. Chem., Int. Ed. 2015, 54,
chemistry approaches toward macrocycles, molecular cages, and 7234−7254.
polymers. Acc. Chem. Res. 2014, 47, 1575−1586. (33) Uptmoor, A. C.; Freudenberg, J.; Schwabel, S. T.; Paulus, F.;
(10) Tashiro, S.; Shionoya, M. Cavity-assembled porous solids
Rominger, F.; Hinkel, F.; Bunz, U. H. F. Reverse engineering of
(CAPSs) for nanospace-specific functions. Bull. Chem. Soc. Jpn. 2014,
conjugated microporous polymers: Defect structures of tetrakis(4-
87, 643−654.
ethynylphenyl)stannane networks. Angew. Chem., Int. Ed. 2015, 54,
(11) Slater, A. G.; Cooper, A. I. Function-led design of new porous
materials. Science 2015, 348, aaa8075-1−aaa8075-10. 14673−14676.
(12) Huang, S. L.; Jin, G. X.; Luo, H. K.; Hor, T. S. A. Engineering (34) Beaudoin, D.; Maris, T.; Wuest, J. D. Constructing monocrystal-
organic macrocycles and cages: Versatile bonding approaches. Chem. - line covalent organic networks by polymerization. Nat. Chem. 2013, 5,
Asian J. 2015, 10, 24−42. 830−834.
(13) Evans, J. D.; Sumby, C. J.; Doonan, C. J. Synthesis and (35) Zhang, Y. B.; Su, J.; Furukawa, H.; Yun, Y. F.; Gandara, F.;
applications of porous organic cages. Chem. Lett. 2015, 44, 582−588. Duong, A.; Zou, X. D.; Yaghi, O. M. Single-crystal structure of a
(14) Hashim, M. I.; Hsu, C. W.; Le, H. T. M.; Miljanic, O. S. Organic covalent organic framework. J. Am. Chem. Soc. 2013, 135, 16336−
molecules with porous crystal structures. Synlett 2016, 27, 1907−1918. 16339.
(15) Hasell, T.; Cooper, A. I. Porous organic cages: soluble, modular (36) Song, Q.; Jiang, S.; Hasell, T.; Liu, M.; Sun, S.; Cheetham, A. K.;
and molecular pores. Nat. Rev. Mater. 2016, 1, 16053. Sivaniah, E.; Cooper, A. I. Porous organic cage thin films and
(16) Das, S.; Heasman, P.; Ben, T.; Qiu, S. Porous organic materials: molecular-sieving membranes. Adv. Mater. 2016, 28, 2629−2637.
Strategic design and structure−function correlation. Chem. Rev. 2017, (37) Carta, M.; Malpass-Evans, R.; Croad, M.; Rogan, Y.; Jansen, J.
117, 1515−1563. C.; Bernardo, P.; Bazzarelli, F.; McKeown, N. B. An efficient polymer
(17) Barrer, R. M.; Shanson, V. H. Dianin’s compound as a zeolitic molecular sieve for membrane gas separations. Science 2013, 339,
sorbent. J. Chem. Soc., Chem. Commun. 1976, 333−334. 303−307.
(18) Simard, M.; Su, D.; Wuest, J. D. Use of hydrogen-bonds to (38) Bushell, A. F.; Budd, P. M.; Attfield, M. P.; Jones, J. T. A.;
control molecular aggregation - self-assembly of 3-dimensional Hasell, T.; Cooper, A. I.; Bernardo, P.; Bazzarelli, F.; Clarizia, G.;
networks with large chambers. J. Am. Chem. Soc. 1991, 113, 4696− Jansen, J. C. Nanoporous organic polymer/cage composite mem-
4698. branes. Angew. Chem., Int. Ed. 2013, 52, 1253−1256.

550 DOI: 10.1021/acscentsci.7b00146

ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

(39) Dechnik, J.; Gascon, J.; Doonan, C.; Janiak, C.; Sumby, C. J. (57) Liu, M.; Little, M. A.; Jelfs, K. E.; Jones, J. T. A.; Schmidtmann,
New directions for mixed-matrix membranes. Angew. Chem., Int. Ed. M.; Chong, S. Y.; Hasell, T.; Cooper, A. I. Acid- and base-stable
2017, DOI: 10.1002/anie.201701109. porous organic cages: Shape persistence and pH stability via post-
(40) McKeown, N. B.; Budd, P. M. Polymers of intrinsic synthetic ″tying″ of a flexible amine cage. J. Am. Chem. Soc. 2014, 136,
microporosity (PIMs): organic materials for membrane separations, 7583−7586.
heterogeneous catalysis and hydrogen storage. Chem. Soc. Rev. 2006, (58) Bera, S.; Basu, A.; Tothadi, S.; Garai, B.; Banerjee, S.; Vanka, K.;
35, 675−683. Banerjee, R. Odd-even alternation in tautomeric porous organic cages
(41) Tian, J.; Thallapally, P. K.; Dalgarno, S. J.; McGrail, P. B.; with exceptional chemical stability. Angew. Chem., Int. Ed. 2017, 56,
Atwood, J. L. Amorphous molecular organic solids for gas adsorption. 2123−2126.
Angew. Chem., Int. Ed. 2009, 48, 5492−5495. (59) Burrows, A. D.; Frost, C. G.; Mahon, M. F.; Richardson, C.
(42) Jiang, S.; Jones, J. T. A.; Hasell, T.; Blythe, C. E.; Adams, D. J.; Post-synthetic modification of tagged metal-organic frameworks.
Trewin, A.; Cooper, A. I. Porous organic molecular solids by dynamic Angew. Chem., Int. Ed. 2008, 47, 8482−8486.
covalent scrambling. Nat. Commun. 2011, 2, 207. (60) Deng, H.; Doonan, C. J.; Furukawa, H.; Ferreira, R. B.; Towne,
(43) Jiang, S.; Jelfs, K. E.; Holden, D.; Hasell, T.; Chong, S. Y.; J.; Knobler, C. B.; Wang, B.; Yaghi, O. M. Multiple functional groups
Haranczyk, M.; Trewin, A.; Cooper, A. I. Molecular dynamics of varying ratios in metal-organic frameworks. Science 2010, 327, 846−
simulations of gas selectivity in amorphous porous molecular solids. 850.
J. Am. Chem. Soc. 2013, 135, 17818−17830. (61) Hasell, T.; Chong, S. Y.; Schmidtmann, M.; Adams, D. J.;
(44) Abbott, L. J.; McDermott, A. G.; Del Regno, A.; Taylor, R. G. Cooper, A. I. Porous organic alloys. Angew. Chem., Int. Ed. 2012, 51,
D.; Bezzu, C. G.; Msayib, K. J.; McKeown, N. B.; Siperstein, F. R.; 7154−7157.
Runt, J.; Colina, C. M. Characterizing the structure of organic (62) Jones, J. T. A.; Hasell, T.; Wu, X.; Bacsa, J.; Jelfs, K. E.;
molecules of intrinsic microporosity by molecular simulations and X- Schmidtmann, M.; Chong, S. Y.; Adams, D. J.; Trewin, A.; Schiffman,
ray scattering. J. Phys. Chem. B 2013, 117, 355−364. F.; Cora, F.; Slater, B.; Steiner, A.; Day, G. M.; Cooper, A. I. Modular
(45) Bennett, T. D.; Cheetham, A. K. Amorphous metal-organic and predictable assembly of porous organic molecular crystals. Nature
frameworks. Acc. Chem. Res. 2014, 47, 1555−1562. 2011, 474, 367−371.
(46) Hasell, T.; Zhang, H.; Cooper, A. I. Solution-processable (63) Schneider, M. W.; Oppel, I. M.; Griffin, A.; Mastalerz, M. Post-
molecular cage micropores for hierarchically porous materials. Adv. modification of the interior of porous shape-persistent organic cage
Mater. 2012, 24, 5732−5737. compounds. Angew. Chem., Int. Ed. 2013, 52, 3611−3615.
(47) Giri, N.; Davidson, C. E.; Melaugh, G.; Del Popolo, M. G.; (64) Tozawa, T.; Jones, J. T. A.; Swamy, S. I.; Jiang, S.; Adams, D. J.;
Jones, J. T. A.; Hasell, T.; Cooper, A. I.; Horton, P. N.; Hursthouse, M. Shakespeare, S.; Clowes, R.; Bradshaw, D.; Hasell, T.; Chong, S. Y.;
B.; James, S. L. Alkylated organic cages: from porous crystals to neat Tang, C.; Thompson, S.; Parker, J.; Trewin, A.; Bacsa, J.; Slawin, A. M.
liquids. Chem. Sci. 2012, 3, 2153−2157. Z.; Steiner, A.; Cooper, A. I. Porous organic cages. Nat. Mater. 2009, 8,
(48) Giri, N.; Pópolo, M. G. D.; Melaugh, G.; Greenaway, R. L.; 973−978.
Rätzke, K.; Koschine, T.; Gomes, M. F. C.; Pison, L.; Cooper, A. I.; (65) Koh, K.; Wong-Foy, A. G.; Matzger, A. J. A porous coordination
James, S. L. Liquids with permanent porosity. Nature 2015, 527, 216− copolymer with over 5000 m2/g BET surface area. J. Am. Chem. Soc.
220. 2009, 131, 4184−4185.
(49) Greenaway, R. L.; Holden, D.; Eden, E. G. B.; Stephenson, A.; (66) El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortes, J. L.; Cote, A. P.;
Yong, C. W.; Bennison, M. J.; Hasell, T.; Briggs, M. E.; James, S. L.; Taylor, R. E.; O’Keeffe, M.; Yaghi, O. M. Designed synthesis of 3D
Cooper, A. I. Understanding gas capacity, guest selectivity, and covalent organic frameworks. Science 2007, 316, 268−272.
diffusion in porous liquids. Chem. Sci. 2017, 8, 2640−2651. (67) Cooper, A. I. Molecular organic crystals: From barely porous to
(50) Yanai, N.; Kitayama, K.; Hijikata, Y.; Sato, H.; Matsuda, R.; really porous. Angew. Chem., Int. Ed. 2012, 51, 7892−7894.
Kubota, Y.; Takata, M.; Mizuno, M.; Uemura, T.; Kitagawa, S. Gas (68) Pulido, A.; Chen, L.; Kaczorowski, T.; Holden, D.; Little, M. A.;
detection by structural variations of fluorescent guest molecules in a Chong, S. Y.; Slater, B. J.; McMahon, D. P.; Bonillo, B.; Stackhouse, C.
flexible porous coordination polymer. Nat. Mater. 2011, 10, 787−793. J.; Stephenson, A.; Kane, C. M.; Clowes, R.; Hasell, T.; Cooper, A. I.;
(51) Mason, J. A.; Oktawiec, J.; Taylor, M. K.; Hudson, M. R.; Day, G. M. Functional materials discovery using energy−structure−
Rodriguez, J.; Bachman, J. E.; Gonzalez, M. I.; Cervellino, A.; function maps. Nature 2017, 543, 657−664.
Guagliardi, A.; Brown, C. M.; Llewellyn, P. L.; Masciocchi, N.; Long, J. (69) Holst, J. R.; Cooper, A. I. Ultrahigh surface area in porous solids.
R. Methane storage in flexible metal-organic frameworks with intrinsic Adv. Mater. 2010, 22, 5212−5216.
thermal management. Nature 2015, 527, 357−361. (70) Chen, L.; Reiss, P. S.; Chong, S. Y.; Holden, D.; Jelfs, K. E.;
(52) Krause, S.; Bon, V.; Senkovska, I.; Stoeck, U.; Wallacher, D.; Hasell, T.; Little, M. A.; Kewley, A.; Briggs, M. E.; Stephenson, A.;
Tobbens, D. M.; Zander, S.; Pillai, R. S.; Maurin, G.; Coudert, F. X.; Thomas, K. M.; Armstrong, J. A.; Bell, J.; Busto, J.; Noel, R.; Liu, J.;
Kaskel, S. A pressure-amplifying framework material with negative gas Strachan, D. M.; Thallapally, P. K.; Cooper, A. I. Separation of rare
adsorption transitions. Nature 2016, 532, 348−352. gases and chiral molecules by selective binding in porous organic
(53) Jones, J. T. A.; Holden, D.; Mitra, T.; Hasell, T.; Adams, D. J.; cages. Nat. Mater. 2014, 13, 954−960.
Jelfs, K. E.; Trewin, A.; Willock, D. J.; Day, G. M.; Bacsa, J.; Steiner, A.; (71) Mitra, T.; Jelfs, K. E.; Schmidtmann, M.; Ahmed, A.; Chong, S.
Cooper, A. I. On-off porosity switching in a molecular organic solid. Y.; Adams, D. J.; Cooper, A. I. Molecular shape sorting using
Angew. Chem., Int. Ed. 2011, 50, 749−753. molecular organic cages. Nat. Chem. 2013, 5, 276−281.
(54) Jie, K.; Liu, M.; Zhou, Y.; Little, M. A.; Bonakala, S.; Chong, S. (72) Kane, C. M.; Ugono, O.; Barbour, L. J.; Holman, K. T. Many
Y.; Stephenson, A.; Chen, L.; Huang, F.; Cooper, A. I. Styrene simple molecular cavitands are intrinsically porous (zero-dimensional
purification by guest-induced restructuring of pillar[6]arene. J. Am. pore) materials. Chem. Mater. 2015, 27, 7337−7354.
Chem. Soc. 2017, 139, 2908−2911. (73) Mastalerz, M.; Schneider, M. W.; Oppel, I. M.; Presly, O. A
(55) Avellaneda, A.; Valente, P.; Burgun, A.; Evans, J. D.; Markwell- salicylbisimine cage compound with surface area and selective CO2/
Heys, A. W.; Rankine, D.; Nielsen, D. J.; Hill, M. R.; Sumby, C. J.; CH4 adsorption. Angew. Chem., Int. Ed. 2011, 50, 1046−1051.
Doonan, C. J. Kinetically controlled porosity in a robust organic cage (74) He, Y. B.; Xiang, S. C.; Chen, B. L. A microporous hydrogen-
material. Angew. Chem., Int. Ed. 2013, 52, 3746−3749. bonded organic framework for highly selective C2H2/C2H4 separation
(56) Kitchin, M.; Konstas, K.; Sumby, C. J.; Czyz, M. L.; Valente, P.; at ambient temperature. J. Am. Chem. Soc. 2011, 133, 14570−14573.
Hill, M. R.; Polyzos, A.; Doonan, C. J. Continuous flow synthesis of a (75) Yang, W. B.; Greenaway, A.; Lin, X. A.; Matsuda, R.; Blake, A. J.;
carbon-based molecular cage macrocycle via a three-fold homocou- Wilson, C.; Lewis, W.; Hubberstey, P.; Kitagawa, S.; Champness, N.
pling reaction. Chem. Commun. 2015, 51, 14231−14234. R.; Schroder, M. Exceptional thermal stability in a supramolecular

551 DOI: 10.1021/acscentsci.7b00146

ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

organic framework: Porosity and gas storage. J. Am. Chem. Soc. 2010, framework for highly enantioselective separation of secondary
132, 14457−14469. alcohols. J. Am. Chem. Soc. 2014, 136, 547−549.
(76) Yan, W.; Yu, X.; Yan, T.; Wu, D.; Ning, E.; Qi, Y.; Han, Y.-F.; Li, (92) Li, P.; He, Y. B.; Arman, H. D.; Krishna, R.; Wang, H. L.; Weng,
Q. A triptycene-based porous hydrogen-bonded organic framework for L. H.; Chen, B. L. A microporous six-fold interpenetrated hydrogen-
guest incorporation with tailored fitting. Chem. Commun. 2017, 53, bonded organic framework for highly selective separation of C2H4/
3677−3680. C2H6. Chem. Commun. 2014, 50, 13081−13084.
(77) Li, B.; Wang, L.; Li, Y.; Wang, D. Q.; Wen, R.; Guo, X. H.; Li, S. (93) Hou, X. D.; Wang, Z. H.; Overby, M.; Ugrinov, A.; Oian, C.;
J.; Ma, L. J.; Tian, Y. Conversion of supramolecular organic framework Singh, R.; Chu, Q. L. R. A two-dimensional hydrogen bonded organic
to uranyl-organic coordination complex: a new ″matrix-free″ strategy framework self-assembled from a three-fold symmetric carbamate.
for highly efficient capture of uranium. RSC Adv. 2017, 7, 8985−8993. Chem. Commun. 2014, 50, 5209−5211.
(78) Yang, W.; Yang, F.; Hu, T. L.; King, S. C.; Wang, H. L.; Wu, H.; (94) Chen, T. H.; Popov, I.; Kaveevivitchai, W.; Chuang, Y. C.;
Zhou, W.; Li, J. R.; Arman, H. D.; Chen, B. L. Microporous Chen, Y. S.; Daugulis, O.; Jacobson, A. J.; Miljanic, O. S. Thermally
diaminotriazine-decorated porphyrin-based hydrogen-bonded organic robust and porous noncovalent organic framework with high affinity
framework: Permanent porosity and proton conduction. Cryst. Growth for fluorocarbons and CFCs. Nat. Commun. 2014, 5, 5131.
Des. 2016, 16, 5831−5835. (95) Luo, X. Z.; Jia, X. J.; Deng, J. H.; Zhong, J. L.; Liu, H. J.; Wang,
(79) Huang, Y. G.; Shiota, Y.; Wu, M. Y.; Su, S. Q.; Yao, Z. S.; Kang, K. J.; Zhong, D. C. A microporous hydrogen-bonded organic
S.; Kanegawa, S.; Li, G. L.; Wu, S. Q.; Kamachi, T.; Yoshizawa, K.; framework: exceptional stability and highly selective adsorption of
Ariga, K.; Hong, M. C.; Sato, O. Superior thermoelasticity and shape- gas and liquid. J. Am. Chem. Soc. 2013, 135, 11684−11687.
memory nanopores in a porous supramolecular organic framework. (96) Liu, M.; Chen, L. J.; Lewis, S.; Chong, S. Y.; Little, M. A.; Hasell,
Nat. Commun. 2016, 7, 11564. T.; Aldous, I. M.; Brown, C. M.; Smith, M. W.; Morrison, C. A.;
(80) Patil, R. S.; Banerjee, D.; Zhang, C.; Thallapally, P. K.; Atwood, Hardwick, L. J.; Cooper, A. I. Three-dimensional protonic conductivity
J. L. Selective CO2 adsorption in a supramolecular organic framework. in porous organic cage solids. Nat. Commun. 2016, 7, 12750.
Angew. Chem., Int. Ed. 2016, 55, 4523−4526. (97) Feng, X.; Ding, X. S.; Jiang, D. L. Covalent organic frameworks.
(81) Zhang, Y.; Zhan, T. G.; Zhou, T. Y.; Qi, Q. Y.; Xu, X. N.; Zhao, Chem. Soc. Rev. 2012, 41, 6010−6022.
X. Fluorescence enhancement through the formation of a single-layer (98) Mohamed, M. H.; Elsaidi, S. K.; Pham, T.; Forrest, K. A.; Schaef,
two-dimensional supramolecular organic framework and its application H. T.; Hogan, A.; Wojtas, L.; Xu, W. Q.; Space, B.; Zaworotko, M. J.;
in highly selective recognition of picric acid. Chem. Commun. 2016, 52, Thallapally, P. K. Hybrid ultra-microporous materials for selective
7588−7591. xenon adsorption and separation. Angew. Chem., Int. Ed. 2016, 55,
(82) Wang, H. L.; Li, B.; Wu, H.; Hu, T. L.; Yao, Z. Z.; Zhou, W.; 8285−8289.
Xiang, S. C.; Chen, B. L. A Flexible microporous hydrogen-bonded (99) Hasell, T.; Schmidtmann, M.; Stone, C. A.; Smith, M. W.;
organic framework for gas sorption and separation. J. Am. Chem. Soc. Cooper, A. I. Reversible water uptake by a stable imine-based porous
2015, 137, 9963−9970. organic cage. Chem. Commun. 2012, 48, 4689−4691.
(83) Yang, W.; Li, B.; Wang, H. L.; Alduhaish, O.; Alfooty, K.; Zayed, (100) Alsbaiee, A.; Smith, B. J.; Xiao, L. L.; Ling, Y. H.; Helbling, D.
M. A.; Li, P.; Arman, H. D.; Chen, B. L. A microporous porphyrin- E.; Dichtel, W. R. Rapid removal of organic micropollutants from
based hydrogen-bonded organic framework for gas separation. Cryst. water by a porous beta-cyclodextrin polymer. Nature 2016, 529, 190−
Growth Des. 2015, 15, 2000−2004. 194.
(84) Sun, Z. Y.; Li, Y. X.; Chen, L.; Jing, X. B.; Xie, Z. G. Fluorescent (101) Evans, J. D.; Huang, D. M.; Hill, M. R.; Sumby, C. J.;
hydrogen-bonded organic framework for sensing of aromatic Thornton, A. W.; Doonan, C. J. Feasibility of mixed matrix membrane
compounds. Cryst. Growth Des. 2015, 15, 542−545. gas separations employing porous organic cages. J. Phys. Chem. C 2014,
(85) Li, P.; He, Y. B.; Zhao, Y. F.; Weng, L. H.; Wang, H. L.; Krishna, 118, 1523−1529.
R.; Wu, H.; Zhou, W.; O’Keeffe, M.; Han, Y.; Chen, B. L. A rod- (102) Swamy, S. I.; Bacsa, J.; Jones, J. T. A.; Stylianou, K. C.; Steiner,
packing microporous hydrogen-bonded organic framework for highly A.; Ritchie, L. K.; Hasell, T.; Gould, J. A.; Laybourn, A.; Khimyak, Y.
selective separation of C2H2/CO2 at room temperature. Angew. Chem., Z.; Adams, D. J.; Rosseinsky, M. J.; Cooper, A. I. A metal−organic
Int. Ed. 2015, 54, 574−577. framework with a covalently prefabricated porous organic linker. J. Am.
(86) Li, B.; Bai, C. Y.; Zhang, S.; Zhao, X. S.; Li, Y.; Wang, L.; Ding, Chem. Soc. 2010, 132, 12773−12775.
K.; Shu, X.; Li, S. J.; Ma, L. J. An adaptive supramolecular organic (103) Jin, Y.; Voss, B. A.; McCaffrey, R.; Baggett, C. T.; Noble, R. D.;
framework for highly efficient separation of uranium via an in situ Zhang, W. Microwave-assisted syntheses of highly CO2-selective
induced fit mechanism. J. Mater. Chem. A 2015, 3, 23788−23798. organic cage frameworks (OCFs). Chem. Sci. 2012, 3, 874−877.
(87) Zhou, H.; Ye, Q.; Wu, X. Y.; Song, J.; Cho, C. M.; Zong, Y.; (104) Smaldone, R. A.; Forgan, R. S.; Furukawa, H.; Gassensmith, J.
Tang, B. Z.; Hor, T. S. A.; Yeow, E. K. L.; Xu, J. W. A thermally stable J.; Slawin, A. M. Z.; Yaghi, O. M.; Stoddart, J. F. Metal-organic
and reversible microporous hydrogen-bonded organic framework: frameworks from edible natural products. Angew. Chem., Int. Ed. 2010,
aggregation induced emission and metal ion-sensing properties. J. 49, 8630−8634.
Mater. Chem. C 2015, 3, 11874−11880. (105) Slater, A. G.; Little, M. A.; Pulido, A.; Chong, S. Y.; Holden,
(88) Xu, S. Q.; Zhang, X.; Nie, C. B.; Pang, Z. F.; Xu, X. N.; Zhao, X. D.; Chen, L.; Morgan, C.; Wu, X.; Cheng, G.; Clowes, R.; Briggs, M.
The construction of a two-dimensional supramolecular organic E.; Hasell, T.; Jelfs, K. E.; Day, G. M.; Cooper, A. I. Reticular synthesis
framework with parallelogram pores and stepwise fluorescence of porous molecular 1D nanotubes and 3D networks. Nat. Chem.
enhancement. Chem. Commun. 2015, 51, 16417−16420. 2017, 9, 17−25.
(89) Tian, J.; Zhou, T. Y.; Zhang, S. C.; Aloni, S.; Altoe, M. V.; Xie, S. (106) Schneider, M. W.; Oppel, I. M.; Ott, H.; Lechner, L. G.;
H.; Wang, H.; Zhang, D. W.; Zhao, X.; Liu, Y.; Li, Z. T. Three- Hauswald, H.-J. S.; Stoll, R.; Mastalerz, M. Periphery-substituted 4 + 6
dimensional periodic supramolecular organic framework ion sponge in salicylbisimine cage compounds with exceptionally high surface areas:
water and microcrystals. Nat. Commun. 2014, 5, 5574. Influence of the molecular structure on nitrogen sorption properties.
(90) Lu, J.; Perez-Krap, C.; Suyetin, M.; Alsmail, N. H.; Yan, Y.; Chem. - Eur. J. 2012, 18, 836−847.
Yang, S. H.; Lewis, W.; Bichoutskaia, E.; Tang, C. C.; Blake, A. J.; Cao, (107) Reiss, P. S.; Little, M. A.; Santolini, V.; Chong, S. Y.; Hasell, T.;
R.; Schroder, M. A Robust Binary Supramolecular organic framework Jelfs, K. E.; Briggs, M. E.; Cooper, A. I. Periphery-functionalized
(SOF) with high CO2 adsorption and selectivity. J. Am. Chem. Soc. porous organic cages. Chem. - Eur. J. 2016, 22, 16547−16553.
2014, 136, 12828−12831. (108) Hasell, T.; Wu, X. F.; Jones, J. T. A.; Bacsa, J.; Steiner, A.;
(91) Li, P.; He, Y. B.; Guang, J.; Weng, L. H.; Zhao, J. C. G.; Xiang, S. Mitra, T.; Trewin, A.; Adams, D. J.; Cooper, A. I. Triply interlocked
C.; Chen, B. L. A Homochiral microporous hydrogen-bonded organic covalent organic cages. Nat. Chem. 2010, 2, 750−755.

552 DOI: 10.1021/acscentsci.7b00146

ACS Cent. Sci. 2017, 3, 544−553
ACS Central Science Outlook

(109) Zhang, G.; Presly, O.; White, F.; Oppel, I. M.; Mastalerz, M. A (130) Little, M. A.; Briggs, M. E.; Jones, J. T. A.; Schmidtmann, M.;
shape-persistent quadruply interlocked giant cage catenane with two Hasell, T.; Chong, S. Y.; Jelfs, K. E.; Chen, L. J.; Cooper, A. I. Trapping
distinct pores in the solid state. Angew. Chem., Int. Ed. 2014, 53, 5126− virtual pores by crystal retro-engineering. Nat. Chem. 2015, 7, 153−
5130. 159.
(110) Li, Q. W.; Sue, C. H.; Basu, S.; Shveyd, A. K.; Zhang, W. Y.; (131) Santolini, V.; Tribello, G. A.; Jelfs, K. E. Predicting solvent
Barin, G.; Fang, L.; Sarjeant, A. A.; Stoddart, J. F.; Yaghi, O. M. A effects on the structure of porous organic molecules. Chem. Commun.
catenated strut in a catenated metal-organic framework. Angew. Chem., 2015, 51, 15542−15545.
Int. Ed. 2010, 49, 6751−6755. (132) Jelfs, K. E.; Eden, E. G. B.; Culshaw, J. L.; Shakespeare, S.;
(111) Taylor, R. G. D.; Carta, M.; Bezzu, C. G.; Walker, J.; Msayib, Pyzer-Knapp, E. O.; Thompson, H. P. G.; Bacsa, J.; Day, G. M.;
K. J.; Kariuki, B. M.; McKeown, N. B. Triptycene-based organic Adams, D. J.; Cooper, A. I. In silico design of supramolecules from
molecules of intrinsic microporosity. Org. Lett. 2014, 16, 1848−1851. their precursors: Odd-even effects in cage-forming reactions. J. Am.
(112) Hasell, T.; Miklitz, M.; Stephenson, A.; Little, M. A.; Chong, S. Chem. Soc. 2013, 135, 9307−9310.
Y.; Clowes, R.; Chen, L.; Holden, D.; Tribello, G. A.; Jelfs, K. E.; (133) Santolini, V.; Miklitz, M.; Berardo, E.; Jelfs, K. E. Topological
Cooper, A. I. Porous organic cages for sulfur hexafluoride separation. J. landscapes of porous organic cages. Nanoscale 2017, 9, 5280−5298.
Am. Chem. Soc. 2016, 138, 1653−1659. (134) Jelfs, K. E.; Wu, X.; Schmidtmann, M.; Jones, J. T. A.; Warren,
(113) Kewley, A.; Stephenson, A.; Chen, L.; Briggs, M. E.; Hasell, T.; J. E.; Adams, D. J.; Cooper, A. I. Large self-assembled chiral organic
Cooper, A. I. Porous organic cages for gas chromatography cages: synthesis, structure, and shape persistence. Angew. Chem., Int.
separations. Chem. Mater. 2015, 27, 3207−3210. Ed. 2011, 50, 10653−10656.
(114) Brutschy, M.; Schneider, M. W.; Mastalerz, M.; Waldvogel, S. (135) Price, S. L. Predicting crystal structures of organic compounds.
Chem. Soc. Rev. 2014, 43, 2098−2111.
R. Direct gravimetric sensing of GBL by a molecular recognition
(136) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.;
process in organic cage compounds. Chem. Commun. 2013, 49, 8398−
O’Keeffe, M.; Yaghi, O. M. Systematic design of pore size and
8400.
functionality in isoreticular MOFs and their application in methane
(115) Berry, D. A.; Ng, K. M. Synthesis of reactive crystallization
storage. Science 2002, 295, 469−472.
processes. AIChE J. 1997, 43, 1737−1750. (137) Price, S. L. Computed crystal energy landscapes for
(116) Jiang, S.; Chen, L.; Briggs, M. E.; Hasell, T.; Cooper, A. I. understanding and predicting organic crystal structures and poly-
Functional porous composites by blending with solution-processable morphism. Acc. Chem. Res. 2009, 42, 117−126.
molecular pores. Chem. Commun. 2016, 52, 6895−6898. (138) Hisaki, I.; Nakagawa, S.; Ikenaka, N.; Imamura, Y.; Katouda,
(117) Liu, J. W.; Chen, L. F.; Cui, H.; Zhang, J. Y.; Zhang, L.; Su, C. M.; Tashiro, M.; Tsuchida, H.; Ogoshi, T.; Sato, H.; Tohnai, N.;
Y. Applications of metal-organic frameworks in heterogeneous Miyata, M. A series of layered assemblies of hydrogen-bonded,
supramolecular catalysis. Chem. Soc. Rev. 2014, 43, 6011−6061. hexagonal networks of C3-symmetric pi-conjugated molecules: A
(118) O’Reilly, N.; Giri, N.; James, S. L. Porous liquids. Chem. - Eur. potential motif of porous organic materials. J. Am. Chem. Soc. 2016,
J. 2007, 13, 3020−3025. 138, 6617−6628.
(119) James, S. L. The dam bursts for porous liquids. Adv. Mater. (139) Diercks, C. S.; Yaghi, O. M. The atom, the molecule, and the
2016, 28, 5712−5716. covalent organic framework. Science 2017, 355, 923−930.
(120) Melaugh, G.; Giri, N.; Davidson, C. E.; James, S. L.; Del (140) Smith, B. J.; Hwang, N.; Chavez, A. D.; Novotney, J. L.;
Popolo, M. G. Designing and understanding permanent microporosity Dichtel, W. R. Growth rates and water stability of 2D boronate ester
in liquids. Phys. Chem. Chem. Phys. 2014, 16, 9422−9431. covalent organic frameworks. Chem. Commun. 2015, 51 (35), 7532−
(121) Zhang, J. S.; Chai, S. H.; Qiao, Z. A.; Mahurin, S. M.; Chen, J. 7535.
H.; Fang, Y. X.; Wan, S.; Nelson, K.; Zhang, P. F.; Dai, S. Porous (141) Evans, J. D.; Jelfs, K. E.; Day, G. M.; Doonan, C. J. Application
liquids: A promising class of media for gas separation. Angew. Chem., of computational methods to the design and characterisation of porous
Int. Ed. 2015, 54 (3), 932−936. molecular materials. Chem. Soc. Rev. 2017, DOI: 10.1039/c7cs00084g.
(122) Zhang, F.; Yang, F. C.; Huang, J. S.; Sumpter, B. G.; Qiao, R.
thermodynamics and kinetics of gas storage in porous liquids. J. Phys.
Chem. B 2016, 120, 7195−7200.
(123) Revelli, A. L.; Mutelet, F.; Jaubert, J. N. High carbon dioxide
solubilities in lmidazolium-based ionic liquids and in poly(ethylene
glycol) dimethyl ether. J. Phys. Chem. B 2010, 114, 12908−12913.
(124) Kang, J. M.; Rebek, J. Acceleration of a Diels-Alder reaction by
a self-assembled molecular capsule. Nature 1997, 385, 50−52.
(125) Evans, J. D.; Huang, D. M.; Haranczyk, M.; Thornton, A. W.;
Sumby, C. J.; Doonan, C. J. Computational identification of organic
porous molecular crystals. CrystEngComm 2016, 18, 4133−4141.
(126) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.;
Eddaoudi, M.; Kim, J. Reticular synthesis and the design of new
materials. Nature 2003, 423 (6941), 705−714.
(127) Desiraju, G. R. Supramolecular synthons in crystal engineering
- A new organic-synthesis. Angew. Chem., Int. Ed. Engl. 1995, 34,
2311−2327.
(128) Hasell, T.; Culshaw, J. L.; Chong, S. Y.; Schmidtmann, M.;
Little, M. A.; Jelfs, K. E.; Pyzer-Knapp, E. O.; Shepherd, H.; Adams, D.
J.; Day, G. M.; Cooper, A. I. controlling the crystallization of porous
organic cages: Molecular analogs of isoreticular frameworks using
shape-specific directing solvents. J. Am. Chem. Soc. 2014, 136, 1438−
1448.
(129) Pyzer-Knapp, E. O.; Thompson, H. P. G.; Schiffmann, F.; Jelfs,
K. E.; Chong, S. Y.; Little, M. A.; Cooper, A. I.; Day, G. M. Predicted
crystal energy landscapes of porous organic cages. Chem. Sci. 2014, 5,
2235−2245.

553 DOI: 10.1021/acscentsci.7b00146

ACS Cent. Sci. 2017, 3, 544−553