Coordination Chemistry Reviews 421 (2020) 213447

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Transport properties in porous coordination polymers

Jet-Sing M. Lee, Ken-ichi Otake, Susumu Kitagawa ⇑
Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Porous coordination polymers (PCPs) have established themselves as an important class of transport
Received 27 April 2020 materials in the last decade. Their high surface area and tailorable porosity have traditionally been taken
Received in revised form 12 June 2020 advantage of for storage, separation, and catalysis applications. Recently, there has been growing interest
Accepted 12 June 2020
in PCP transport, which include electron, proton, and anion/cation conduction, in addition to the trans-
port of neutral molecules. This perspective highlights both current methodological breakthroughs and
our proposed terms: (1) integration, (2) dynamic, (3) anisotropy, (4) disorder, and (5) dimensionality
Keywords:
modulation, as important concepts for future transportive PCPs.
Porous coordination polymers
Metal–organic frameworks
Ó 2020 Elsevier B.V. All rights reserved.
Conductivity
Electric
Proton
Ionic
Mass transport

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Electrical conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Proton conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Anion/Cation conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5. Mass transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
6. Perspectives and outlooks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

1. Introduction coordination polymers (PCPs) [1], also known as metal–organic

frameworks (MOFs) [2], have attracted intense interest due to their
The transport phenomenon is one of the most important func- structural diversity and designable porosity, and thus, have
tions of materials. Transport of electrons, charges (ions), and mole- become a strong platform on which to develop these transportive
cules within matter is ubiquitous. It is important that transport materials (Fig. 1).
materials with high efficiency and selectivity, materials with aniso- There are currently > 75,000 unique PCPs occupying ~ 9% of the
tropic transport functions, and electrically conductive materials Cambridge Structural Database [3,4]. This relatively new class of
coupled with several functions, be developed in the future. Porous porous materials consist of metal ions/clusters, known as sec-
ondary building units (SBUs), and organic ligands interconnected
by coordination bonds that typically form crystalline frameworks
⇑ Corresponding author.
with long-range order [1,5]. A versatile range of synthetic
E-mail address: kitagawa@icems.kyoto-u.ac.jp (S. Kitagawa).

https://doi.org/10.1016/j.ccr.2020.213447
0010-8545/Ó 2020 Elsevier B.V. All rights reserved.
2 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
Fig. 1. Classes of PCPs with transport properties: electron, proton, ion, and mass; and their potential applications.
Fig. 2. The number of yearly published articles containing the keywords ‘‘conduct-
ing/conductive/conductivity/diffusion coefficient” and ‘‘porous coordination poly-
mers/metal–organic frameworks/MOFs”, surveyed by SciFinder. The terms
containing ‘‘conductivity” was refined due to the high number of irrelevant results.
Accessed 15th October 2019.
approaches has been developed since they were first reported
[6,7], allowing for the development of targeted structures through
a choice of building blocks for respective applications. However, for
electronic applications, the presence of large framework voids and
nodes generally results in insulating PCPs, and it took around a
decade to successfully tackle this challenge in early examples of
PCPs [8]. Over the ensuing years, design rules were developed,
allowing for the study of a steadily growing number of electrically
conducting PCPs (Fig. 2). Similarly, it took around a decade for
examples of ion conductivity to be shown as possible in PCPs
[9,10]. Strategies that introduced an ion-hopping pathway into
the solid-state enabled the use of PCPs in further applications, such
as in electrolytes for batteries and fuel cells, gas sensors, solar cells,
and bipolar resistors [9,11,12].
The ease of PCP designability makes it an attractive platform on
which to develop transportive materials. For example, a plethora of
candidates can arise by combining varying multivalent metal ions
of differing redox activities with a near-endless variety of func-
tional or dynamic organic ligands. Furthermore, frameworks and
pore functionalities can lead to concerted functionality. It has
now been just over a decade since the era of conducting PCPs
began. Here, we discuss the main breakthroughs in this area and
provide direction for the next generation of materials.
2. Electrical conductivity
With an ever-growing need for more power and energy in mod-
ern society, new functional materials need to be developed. Tradi-
tional approaches to realize electrical conductivity required
extrinsic doping of existing materials, which has limitations. How-
ever, the designability of PCPs at the molecular level offers a pow-
erful method for tailoring their properties. In 1986, a conductive
3D coordination polymer possessing a high conductivity of 103 S
cm
1 at room temperature was reported using [Cu(2,5-dimethyl-
DCNQI)2] (DCNQI = N,N0 -dicyanoquinonediimine); [13] however,
permanent porosity was not realized. Here, the Cu ions have an
average oxidation state of + 1.33 and the structure contains seven
interpenetrating diamond nets with infinite stacks of DCNQI radical
anions. Although such early reports of conducting frameworks were
made, PCPs that possess both permanent porosity and electrical
conductivity were not identified until decades later. The majority
 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
of PCPs are insulators (conductivities < 10
10 S cm
1) due to the
absence of low-energy charge transport pathways, [14] resulting
in many of these exhibiting a lack of mobility in the charge carri-
ers[15]. Typically, the energy difference between the orbitals of
the metal ions and the ligands in conventional PCPs makes it chal-
lenging to obtain a highly conductive material. In addition, the por-
ous structure of PCPs results in large distances between linkers,
which restrict p–p stacking [16] and lead to poor orbital overlap,
which keeps the electrons in a highly localized state. Because con-
ductivity (r) has a linear correlation with both charge carrier
mobility (l) and carrier density (n), the rational design of architec-
tures and components to enhance the physical parameters of both l
and n is essential to realize high electrical conduction. To achieve
high charge mobility, long-range charge transport pathways must
be established through the entire PCP crystal. Thus, the choice of
organic and inorganic building blocks is important. For example,
the hardness/softness of metal ions and the choice of coordinated
heteroatom ligands greatly affects electron transfer ability. Whilst
needing to attain high carrier densities, it is also important to con-
sider the redox activity of the ligand or the metal centre. To aid this,
a doping strategy can be employed for additional control of electron
and hole concentrations.
Two main factors affect the resultant electrical conductivity of a
PCP: its structural architecture and the components used to build
the framework. The type of architecture can be categorized into
three classifications.
I. Intrinsic conductivity from the framework. Electric conduc-
tivity arises from the framework itself, such as through the
metal–ligand bond, [17–19] ligand-to-ligand, [20–22] or a
combination of both [23] However, porosity is not required
here, as exemplified by non-porous [Cu(2,5-dimethyl-
DCNQI)2] described earlier [13].
II. Guest-induced conductivity that assembles in the pores/
channels of the framework. Nanopores of the PCP can be
loaded with an electroactive guest, such as 1D conducting
polymers [24,25]. The porosity and conductivity can then
be modulated by controlling the amount of monomer loaded
into the framework before polymerization.
III. Conductivity through framework-guest synergy. Guests can
enter the pores and interact directly with the framework,
thereby installing or enhancing the electrical conductivity of
the framework. For example, 2,5-dihydroxybenzoquinone
(DHBQ), an electroactive ligand previously used in an intrinsi-
cally conducting (Classification I) Fe-based PCP [26], can
potentially coordinate to vacant Zr sites of insulating PCN-
700. The system exhibits good energy level matching, allow-
ing for a charge transfer pathway through Zr clusters and
installed DHBQ linkers [27]. It is well known that coordination
polymers of 7,7,8,8-tetracyanoquinododimethane (TCNQ)
with transition metal ions, in particular, copper ions, provide
electrically conducting materials, although their single crys-
tallographic structures have rarely been obtained [28–31].
Based on the background of this chemistry, TCNQ molecules
have been incorporated into thin films of [Cu3(BTC)2] (BTC =
benzene-1,3,5-tricarboxylic acid, framework also known as
HKUST-1), suggesting the formation of guest bridges with
copper paddlewheels [32,33]. Since these compounds are
multi-component systems, it is difficult to characterize them,
as these materials often contain defects and disorder. How-
ever, developing this type of chemistry is of great significance
to opening new applications for porous materials.
The various components for building electrically conductive
PCPs are summarized in Fig. 3. Initially, external approaches were
attempted, such as post-synthetic insertion of an external redox-
3
active guest into the pores (Fig. 3a) [32,34–36] or forming compos-
ite structures with existing electrically conductive materials
(Fig. 3b) [24,25,37]. Lately, design strategies have allowed intrinsic
electrical conductivity in PCPs without the presence of another
material (Classification I) established via through bond (Fig. 3c)
[8,17,38–40] or through space approaches (Fig. 3d) [20–22]. Vari-
ous research groups have recently published excellent reviews
detailing these works [14,33,41,42], so we will not discuss these
in detail here. However, in particular, the method for constructing
2D PCPs with square planar metal centres and p-conjugated
ligands is a significant approach for yielding highly conducting
PCPs (Fig. 3e) [43–54].
2D p-conjugated PCPs are considered analogous to graphene
[50], and exhibit high electrical conductivity due to full charge delo-
calization along the 2D plane [49]. Conductivities of up to ~ 10 S
cm
1 for bulk compressed pellets utilizing a coronene ligand [52]
and up to 40 S cm
1 for thin films based on a triphenylene PCP
[50] have been reported at room temperature. These conductivities
are some orders of magnitude higher than the conductivities of
PCPs formed using other methods. This has led many researchers
to focus on this strategy and simply vary the metal centre or the
coordination bondable heteroatom on the linker. Therefore, possi-
bilities for this approach will soon be exhausted, so researchers
should find a new method to broaden this horizon. Simply expand-
ing the size of the ligand (e.g., from coronene to hexabenzo-
coronene) may lead to insolubility issues in addition to greater
synthesis difficulties. Protocols should be developed to also investi-
gate varying the electronic structures of the ligand, for example, by
embedding heteroatoms within the p-conjugated ligands. This may
lead to stronger interactions between the metal centre and the
ligands. Regarding increasing the p-conjugation size to expand
the library of ligands, specific sites of the ligand could instead be
enlarged. For instance, the core or end parts of the popularly used
triphenylene ligand could be expanded specifically (e.g., from a ben-
zene core to phenalene or benzene ends to naphthalene). This may
result in stronger packing interactions between the 2D PCP layers
and lead to an improvement in crystal growth or conductivity. Both
of these strategies are widely known to affect non-covalent interac-
tions in organic electronics [57,58]. A recently reported mixed
ligand approach to 2D p-conjugated PCPs extends the horizon for
tuning electrical conductivity and porosity [59]. This could poten-
tially be further expanded to ligands with differing shapes, sizes,
or functional groups, to yield new functional materials.
3. Proton conductivity
Materials that can conduct protons (H+) are of importance in
applications such as fuel cells, which currently utilize ionomeric
polymers. Nafion, a sulfonated fluoropolymer, was discovered in
the late 1960s and is still used today. However, it requires high rel-
ative humidity (RH) to perform well, and the polymer is not stable
above 80 °C. PCPs have potential for the development of new H+
conductors as they are stable at higher temperatures and allow
the accommodation of guest molecules in the pores. Additionally,
variances in physical structure can be utilized, such as phase-
separated, [60] solid-solution, [61] defect-tunable, [62] and flexible
structures [63,64]. H+ conductivity, r, can be expressed by the
equation: r = nel, where n is the mobile H+ density, e is the ele-
mentary charge, and l is H+ mobility. Thus, a combination of a high
H+ source and a good conduction pathway is required for high con-
ductivity. To increase n in PCPs, the design of the H+ source, either
via an acidic moiety of the framework or acidic guests inside the
pores, must be considered. A high pKa H+ source can enhance H+
conduction. For H+ to migrate efficiently (or to increase l), the con-
duction pathway along sites must be separated by a small energy
4 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447

Fig. 3. Various components used to produce electrically conducting PCPs. (a) Dopant: ferrocene [34], iodine [35], redox-active conjugated guest [32]. Air can also work as an
oxidant [55,56]. (b) Composites: conducting polymers [24,25], carbonaceous materials [37]. (c) Through bond: 2D sheet conduction pathway [8], short MM distance [17], 1D
M-S conduction pathway [38–40]. (d) Through space: short SS distance between p-p stacked layers [20], p-p stacking along 1D polymer [21], p-p stacking in a 2D layer [22].
(e) p-conjugated 2D structures: benzene [43–48], triphenylene [49–51], coronene,[52] phthalocyanine [53,54]. Coordination bonding points of ligands (blue) with metal ion
(red) are highlighted.

Fig. 4. Types of anhydrous H+ conductors. (a) External molecule incorporation into the PCP nanochannels with high mobility [11]. (b) intrinsic conductivity of a non-porous o-
CP via H+ hopping on ligands coordinated to the CP [72].

barrier and with equal H+ affinity. The ability of molecular-level Although this perspective focuses on PCPs, it is noteworthy to
design in PCPs can be a powerful tool, for example, by decorating introduce non-porous, coordination polymers (CPs) here as they
the crystalline structure with acidic groups that possess regular have similar components to PCPs, and in some cases, better H+ con-
spatial separations. ducting properties (discussed later). There are two types of CPs:
 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
organic ligand-bridged CPs (o-CPs) and inorganic CPs (i-CPs). Both
types predate the discovery of PCPs [65,66].
Early design principles for introducing H+ carriers into PCPs
involved: direct introduction as counterions in the framework
voids, covalent attachment of acidic groups onto the framework,
or incorporation of acidic groups into the pores [9]. A (NH4)2
(adp)[Zn2(ox)3]3H2O framework (adp = adipic acid and ox =
oxalate) that utilized these strategies showed a H+ conductivity
of 10
2 S cm
1 at room temperature under 98% RH. [9] A decreased
H+ conductivity observed at lower RH suggested that water plays
an important role in creating the H+ conduction pathway. Various
methods have been utilized to increase the H+ conductivity of PCPs
in humid systems, such as controlling defects [67] and the addition
of strong acids [68] to name a few. Research in the area of hydrated
H+ conductors is well established, therefore, we would like to high-
light recent reviews [69,70] which covers this type of H+ conductor
more extensively.
Completely humid-free, anhydrous proton conductors have
potential advantages over their traditional hydrated counterparts.
For instance, controlled humidity is not required in the cell, and
more importantly, operating temperatures above the boiling point
of water are possible, which leads to: (a) a higher activity of the
fuel cell catalyst; (b) a greater tolerance to Pt catalyst poisoning,
as the affinity with CO side products is reduced; and (c) a
decreased volume of the on-board fuel cell, as a simpler cooling
system is used. Thus, the discovery of potential H+ carriers that
do not contain water is of central importance (Fig. 4). One
candidate—imidazole—was demonstrated by encapsulating the
molecule into the PCP nanochannels and showed anhydrous H+
conductivity.[11] The dynamic nature of imidazole allows for
increased H+ mobility and exhibits conductivity at a high temper-
ature of 120 °C. In the same year, a similar molecule, 1H-1,2,4-
triazole, also showed promise as an anhydrous H+ conductor when
loaded into a sulfonate-lined PCP [12]. Recently, modulation of the
PCP-guest interaction was demonstrated using a flexible PCP with
photoswitchable azobenzene moieties [71]. The azobenzene units
protrude into the pores and can switch between trans and cis iso-
mers which result in increased and reduced conductivities, respec-
tively, due to controlling the interactions with the guest molecules.
Fig. 5. Examples of ion conductivity strategies. (a) Free mobile ions with grafted counterions to the framework [77]. (b) Encapsulation of salts/ionic liquids with one ion of the
pair interacting with framework allowing for separation and mobility of the counterion [78]. (c) Incorporation of conducting polymers and salts into framework
nanochannels, allowing for fluid-like motion in the pores [79].
5
All of the strategies discussed above rely on the formation of hybri-
dized composite conductors, whereas, anhydrous H+ conductors
that conduct intrinsically in the framework are still rare.
In 2012, phosphate groups were shown to be able to create
guest-free anhydrous intrinsic H+ conduction in a non-porous [Zn
(H2PO4)2(TzH)2] (TzH = 1H-1,2,4-triazole) o-CP [72]. The network
consisted of octahedral Zn2+ with monocoordinated orthophos-
phate and bridging TzH which formed parallel 2D sheets that acted
as the conduction pathway. A non-porous i-CP network that con-
tains two types of orthophosphates also showed anhydrous H+
conduction with [Zn(HPO4)(H2PO4)2](ImH2)2 (ImH = imidazole)
[73]. This material exhibited ‘‘plastic crystal” behaviour—a long-
range-ordered crystal structure with a short-range disorder—and
could reorient in the solid-state. A non-linear increase in conduc-
tivity was observed above ~ 55 °C, which was attributed to an
acceleration of the motion of active ImH+2. Melting occurred at
160 °C, but crystallinity was retained upon cooling, which showed
that these materials can also exhibit dynamic behaviour in the
solid-state. Disordered and defective PCPs and CPs have great
potential to expand the chemistry of this area [74]. For example,
an amorphous glass of an o-CP, [Cd(1,2,4-triazole)2(H2PO4)2],
showed a H+ conductivity several orders of magnitude higher than
its crystalline equivalent [75].
4. Anion/Cation conductivity
Ionic conductors are of key importance in energy applications.
For example, anion conductors can be used as electrolytes in fuel
cells, which avoids the use of precious metal catalysts, and cation
conductors can be used as solid-state electrolytes in batteries.
The ability to design and utilize the regular pores of PCPs for ion
motion makes them advantageous compared to conventional liq-
uid electrolytes and organic polymers. Ion conductivity in PCP pore
architectures can be separated into three classifications (Fig. 5).
I. Static anionic or cationic metals in the framework with
mobile counter cations or anions, respectively. For anionic
conductors, these usually involve the free motion of the
charge balancing anions coordinated to SBUs [76]. In catio-
6 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
nic conductors, the organic portion of a salt is commonly
grafted to the PCP to allow for the freedom of the cation,
whilst the organic anion is anchored [77].
II. Encapsulation of salts or ionic liquids. The inclusion of these
can result in both cations and anions being mobile, which
reduces the overall transference numbers to one of the sides.
Thus, careful control of the interactions between the PCP
surface with salts/ionic liquids can free the pairs, for exam-
ple, by having a stronger interaction with one ion to allow
conduction of the counterion [78].
III. Insertion of conducting polymers into the pores. PCP pore
channels can be used to host ion conductive polymers that
possess liquid-like free motion [79]. This combines the
dynamic properties of the polymer guests with directional-
ity and robustness from the solid host framework to allow
the creation of order from disorder.
Classification I ion conductors consist of cationic or anionic
frameworks where counterions exist in the pore spaces that typi-
cally result in a densely packed system. In most frameworks fitting
this description, the counterions cannot move; therefore, they can-
not be considered as an ion conductor. Such densely packed systems
with non-mobile ions filling the space are also not classed as porous
materials. A porous cationic/anionic framework structure with
dynamic ions in the cavities is a prerequisite for ion conductors.
One such structure was achieved by post-synthetic grafting of
LiOtBu to the zirconium (Zr) node of a UiO-66 framework (Fig. 5a),
resulting in a Li+ conductivity of 1.8  10–5 S cm
1 at 293 K [77].
In 2014, the first example of a Classification II ion conductor
was demonstrated with an alkaline-stable ZIF-8 (ZIF = zeolitic imi-
dazolate framework) OH
conductor using a method analogous to
the early reports of H+ conductors [76]. The strategy involved
either introducing OH
as a counter anion into the PCP pores or
inserting OH
salts into the voids by encapsulating tetrabutylam-
monium hydroxide salts in the pores. The OH
ions are exchange-
able, and an ionic conductivity of 2.3  10–8 S cm
1 (99% RH) was
observed for the NBu4OH-included sample. Increased conductivi-
ties were observed at higher RH, suggesting that the ionic conduc-
tivity was enhanced by the diffusion of OH– ions and not the
diffusion of aprotic NBu+4 ions. It is important to match the interac-
tions of a PCP framework with inserted salts for good performance.
For example, the supramolecular interaction of an FJU-66 frame-
work with planar [EVIm]+ cations allowed the [EVIm]+–OH
pairs
to be pulled far apart, which freed the OH
anions for high conduc-
tivity, even when compared with higher concentrations of other
salts within the same framework [78]. Consideration of the frame-
work redox potential is also important. Oxidative reversible inser-
tion of weakly coordinating anions, BF–4 and PF–6, into a redox-active
PCP allows for high specific energy, which can be utilized in a dual-
ion battery [80]. The nanochannels of PCPs can be employed to
carry poly(ionic liquids) which can act as OH– ion carriers for use
in alkaline anion exchange membranes. This method can result
in higher conductivities of up to six orders of magnitude greater
than that of the pristine PCP [81]. Defects in PCPs are also able to
enhance anion conductivity. For instance, it was shown that a
PCP that contained missing-linker defects via post-synthetic mod-
ification with KOH allowed a four-orders-of-magnitude increase in
conductivity compared to the pristine material [82]. An interesting
strategy was reported that involved stripping away anions in a
neutral framework to create a cationic PCP with mobile halogen
counterions [83]. The halogen anions could later be exchanged
with OH– ions to allow for OH– conductivity. Recently, a Zr-based
UiO-66 derivative with nanochannels selective for F
over Cl
,
Br
, I
, NO
2


3 , and SO4 was developed [84]. The F ions were con-
ductive, with a conductivity of up to ~ 10 S m
1 observed, allowing
for potential use in water defluoridation.
Various conducting cations in PCPs have been reported, such as
Li+, [10,77,85–90] Na+, [89] Mg2+,[89–92] and Al3+ [90]. Traditional
linear polymers, such as polyethylene glycol (PEG), conduct Li+ but
in a bulk disordered state. In 2011, an example of a Classification III
ionic conductor was demonstrated with the confinement of a PEG-
Li salt complex in the PCP pores, allowing for high mobility of the
PEG chains in sequential motion: the confined PEG allowed move-
ment of Li+ in the constrained 1D channels [79]. This combination
resulted in liquid-like, high mobility with the use of a solid mate-
rial. In the same year, a salt inclusion method was demonstrated by
the uptake of LiOiPr which allowed for Li+ conduction in [Mg2(dob-
dc)] (dobdc4– = 1,4-dioxido-2,5-benzenedicarboxylate) [10]. The
framework 1D channels, with diameters of ~ 14 Å, are lined with
coordinatively unsaturated Mg2+ cations that graft to the alkoxide
anions, allowing the free movement of Li+. Strong anion interac-
tions with PCP metal ions can also allow for conductivity by weak-
ening the anion-cation coordination environment [86]. A post-
synthetic functionalization approach to the SBU is a route to Li+
conduction. An example was shown by first dehydrating the
framework which yielded open sites to then graft LiOtBu [77]. This
method resulted in a significantly lower activation energy for ion
conduction than if Li+ was introduced via deprotonation. Another
interesting approach for modification was exhibited by partially
replacing the trivalent metal ions of the framework (Sc3+) with
divalent metal ions (Cd2+ and Mn2+), allowing for the addition of
mobile monovalent cations. This increased the conductivity by
one order of magnitude [87]. The direct synthesis of PCPs that con-
tain Li+ in the framework is a potential approach to achieve high
loading. This was demonstrated using an anionic aluminium
framework with Li+ counterions, Li[Al(C6H4O2)2], in which the
highest Li+ loading was obtained for a PCP of 2.50 wt% [88]. An
eight-fold increase in ionic conductivity between the crystalline
framework and an amorphous equivalent was observed, showcas-
ing the benefits of crystallinity.
5. Mass transport
Mass transport properties are essential functions of PCPs
because they are required for most associated applications, such
as gas storage, the separation of gases, sensors, and catalysis. In
these applications, the interaction of guest molecules in the pores
with the framework is crucial. Therefore, it is important to under-
stand and quantify the transport of the guest molecules through
their nanoscopic channels. In particular, the selectivity of the guest
adsorption/separation is important, and is achieved by the differ-
ing transport rates of the chemical species through the pores.
One use of such kinetic separations is practiced commercially for
the N2/O2 separation from air using a pressure-swing adsorption
process [93].
The physical parameter of mass transport, known as the self-
diffusion coefficient (D), is important to consider. Self-diffusion in
porous materials can be divided into three components: molecular
diffusion, Knudsen diffusion, and surface diffusion [94,95]. The
molecular diffusion process, which is predominant in solids with
large pores, is interpreted as molecular motion, where a large num-
ber of collisions between molecules take place. Knudsen diffusion
occurs as a result of the collisions of guest molecules with pore
walls in a nanoporous system. Surface diffusion involves the
adsorption and subsequent diffusion of molecules by hopping
along the surface of a porous media. Under certain conditions, this
can enhance the total diffusion. The dominant mechanism of diffu-
sion changes depending on the temperature, pressure, and
strength of the host–guest interaction.
Several techniques are available for the experimental quantifi-
cation of mass transport in PCPs, such as quasi-elastic neutron
 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
scattering (QENS) [96], pulsed-field gradient nuclear magnetic res-
onance (PFG-NMR), [97] interference microscopy (IFM), and infra-
red microscopy (IRM) [98,99]. Other techniques such as
luminescence quenching, [100] quartz-crystal microbalance
(QCM), [101,102] and confocal laser scanning microscopy
[103,104] provide diffusion coefficients in both the liquid and
gas-phases.
Since the development of experimental quantification methods,
joint experimental and computational investigations of guest
transport in PCPs have been conducted. Early examples include dif-
fusion studies of n-alkanes in IRMOF and MIL-47, [105,106] ben-
zene in MOF-5 [97], methane in HKUST-1 [107], and methane
and carbon dioxide in UiO-66 [108]. These studies primarily
focused on the adsorption equilibrium state, namely, the pore
capacity, surface area, and guest affinity. Assuming that the struc-
ture is rigid, it is possible to quantitatively predict the host–guest
interactions and guest transport properties in ‘‘robust” PCPs. How-
ever, the situation gets more complicated in the case of flexible-
type PCPs, which exhibit structural changes upon guest inclusion
[109]. Flexible PCPs are considered particularly suitable for sepa-
rating mixtures of substances with similar properties because of
the guest triggered structural transformation [1,63,110–112].
However, computational interpretations and predictions of guest
molecule transport properties in flexible PCPs remain unexplored
[113,114]. Their ‘‘soft” porosity offers new functionality and
another design rationale using kinetic control that is unachievable
with conventional open and rigid frameworks [115–119].
A self-accelerating adsorption process was demonstrated in the
pore of a [Cu(aip)(H2O)] (aip = 5-azidoisophthalate) PCP, allowing
unprecedented selective adsorption of CO over N2 [115]. Weak
adsorption of CO on the Cu2+ site induced marked global structural
change, creating additional space that allowed further adsorption
of CO, thus, resulting in reversible self-accelerating CO adsorption
(Fig. 6a) [115]. A differing flexible PCP, DUT-49, exhibited the first
Fig. 6. Examples of new transport behaviours of flexible-type PCPs. (a) Self-accelerating CO transport caused by the global structural change from closed to open framework
[115]. (b) Diffusion-regulatory gate functionality due to the dynamic aperture [118].
7
spontaneous desorption of gas during increasing applied pressure,
described as negative gas adsorption [116]. This adsorption beha-
viour was controlled by a sudden hysteretic structural deformation
and pore contraction in the PCP that released the guest molecules.
Recently, it was shown that high selectivity in guest transport
could also be achieved by exploiting local dynamic motions. The
local motions of dynamic entities in the pore of PCPs render them
adaptive, and thus, responsive to external stimuli. An anion pil-
lared PCP, ZrFSIX-2-Zn-i, with embedded ‘‘molecular rotors” on a
pyridine framework afforded a size-selective channel for carbon
dioxide from methane and N2 under ambient conditions by the
controlled rotation behaviour.[117] A thermally responsive PCP,
[Cu(OPTz-ipa)] (OPTz = phenothiazine-5,5-dioxide), incorporated
a ligand with a butterfly-type flipflop vibrational moiety (OPTz)
at the channel wall intercepting the guest diffusion path
(Fig. 6b).[118] The guest diffusion process of the PCP was impeded
by the temperature-regulated gate of the intercepted channel,
allowing for high separations of O2/Ar and ethylene/ethane.
[Cu2(BTR)2]2NO3 (BTR = 4,4’-bis[1,2,4-triazole]) exhibits a unique
thermoresponsive gating adsorption behaviour that depends on
the thermal motion of the extraframework counterions [119].
Flexible PCPs that respond to light have high potential in this
field [120–123]. By incorporating a photoresponsive module
within the framework, switchable mass transport properties can
be bestowed to the PCP. An early example of this is PCN-123, which
contains a photoresponsive azobenzene group within a rigid
framework [121]. The azobenzene group exhibits trans–cis isomer-
ization upon UV light irradiation that triggers a decrease in the gas
uptake. However, due to the steric hindrance of azobenzene groups
in the cavity and low light penetration, PCN-123 suffered from a
slow response toward the light irradiation, thus, requiring several
hours of irradiation. Another strategy is to use a photoresponsive
ligand that allows collective flexibility to the framework.
This was achieved by using a dithienylethene-based ligand in
8 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
[Zn2(bdc)2(Lo)] (bdc = benzenedicarboxylic acid and Lo = bis(pyri
dyl)dithienylethene) which resulted in quantitative and reversible
isomerization [122]. [Zn2(bdc)2(Lo)] has a twofold interpenetrated
framework that exhibits switchable capacity and gate-opening
behaviour upon irradiation of UV or visible light. An interesting
strategy for modulated guest uptake was demonstrated by using
a two-component core–shell UiO-68 type PCP, with the interior
designed for efficient guest uptake surrounded by a thin photore-
sponsive outer shell [123]. It was shown that the azobenzene
ligand shell acts as a switchable kinetic barrier for the diffusion
to the MOF interior. Such integrated heterostructures that combine
PCPs with differing properties are promising for developing future
multifunctional materials.
An important aspect to realize PCPs in actual mass transport
applications but often overlooked is the utilized macroscopic form
of the material [124]. Powdery PCPs are not suited for industrial
use due to their dustiness and inevitable pressure drop in fluid flow
applications. Several approaches have been investigated, with the
simplest being pelletization of the PCPs. Although the high pres-
sure required during the pelletization process sometimes alters
or destroys the porosity of the PCP, suitable choices of binders
and/or lubricants can retain even the dynamic properties of flexible
PCP systems [125]. Other methods based on granulation, [126]
extrusion, [127] or spray drying [128] are also well studied due
to the relative ease of their scale-up. The liquid phase epitaxy
(LPE) method for controlled PCP growth on a metal or oxide sup-
port [129] is also a promising approach as the LPE method allows
for designable architectures [130]. Recently, mixed-matrix mem-
branes (MMMs) that incorporate PCPs as the filler are gaining
interest due to the combined advantages of using a flexible
polymer matrix with a highly porous filler [131]. Numerous
PCP-based MMMs have been prepared and applied in various
applications including gas separation, nanofiltration, and solid
electrolytes [132,133]. Detailed discussions on these shaping
methods are beyond the scope of this perspective, therefore, we
encourage readers to refer to the above-mentioned references to
gain a greater insight.
As discussed in these state-of-the-art examples, soft porosity
enables pore shape adaptability and alteration of the guest dynam-
ics. By designing a photoresponsive moiety within the framework,
mass transport can be modulated by an external switch. The ease
of PCP designability makes it an attractive platform from which
to develop selective separation media utilizing the different diffu-
sivity of guests inside the pores. It is important, however, for
researchers to know that obtaining the desired PCP is not the
end of the story. The macroscopic morphology of the material
should be considered for practical use to make a real impact.
6. Perspectives and outlooks
The exploration of the transport properties of PCPs has been
extensive. In particular, the rise of conductive PCPs has allowed
for many potential applications such as in sensors, [134–136]
supercapacitors, [137–139] chemical capture and release, [140]
electrochromism, [141–143] electrocatalysis, [53,144,145] transis-
tors, [43,146,147] fuel cells, [148–150] ion emitters, [151] and bat-
tery electrolytes [10,86,91,152]. The structural and compositional
tunability of PCPs allows for the rational design of materials at
the molecular scale, which is not usually possible with traditional
materials in these applications. Although high performing PCPs are
often reported, the materials are essentially useless if they are not
stable. This is, unfortunately, a major issue with PCPs as many are
easily hydrolysed and the presence of liable coordination bonds
often leads to decomposition [153]. Conducting applications are
generally performed under harsh and non-ideal lab conditions.
For example, electrochemical sensing and resistive sensing appli-
cations may require use in humid/aqueous conditions that already
exclude many PCP candidates. Electrocatalytic applications such as
oxygen reduction, oxygen evolution, hydrogen evolution, and car-
bon dioxide reduction reactions, require tolerance in a wide elec-
trolyte pH range. 2D electrically conducting PCPs have potential
in these areas, with reports of excellent stability in strongly acidic
and alkaline aqueous solutions [139,144]. A requirement for super-
capacitors is that they must be stable for over tens of thousands of
charge–discharge cycles. Electrically conducting PCPs have
recently found breakthroughs in this area, with high capacitance
retention achieved for over 10,000 cycles and areal capacitances
that outperform nearly all other materials [137,139]. Anhydrous
PCP H+ conductors allow access to high-temperature operations
above 100 °C, [11,12] which breaks the barrier for what is possible
with existing technology and makes the discovery of higher cat-
alytically active fuel cells possible. We would like to highlight
the fact that claiming structural stability requires rigorous charac-
terizations. A broadened powder X-ray diffraction after conduction
measurements is not proof of structure retention. In fact, degrada-
tion of the PCP may result in enhanced conduction due to dissolu-
tion and liberation of ions, which is not an inherent property of the
PCP. We suggest that future researchers demonstrate stability with
reproducible conduction results as more definitive proof.
Regarding the mass transport properties of PCPs, the kinetic
behaviours of guest molecules have not been well explored in
flexible-type PCPs compared to those of their rigid counterparts.
Typically, flexible PCPs exhibit poor designability and controllabil-
ity. More development in both experimental and computational
investigations will open up new opportunities.
It is important to transition away from the classic design rules
of PCPs to realize new properties and enhanced functionality. We
propose that the future research direction in this field includes
the following (Fig. 7).
(1) Individual ? Integrated. Currently, simple and singular
components are used in frameworks to realize bulk conduc-
tion. We could combine differing components, such as metal
ions, ligands, or separate PCPs, to expand and discover new
materials. The integration of metal ions or ligands in a solid
solution can be used to fine-tune or provide synergistic
properties [59,154]. Macroscale integration in core–shell/bi-
layers creates a heterointerface that may exhibit unique con-
duction behaviour. Control of this interface may lead to
increased conductivity, with this phenomenon termed
‘‘nanoionics” [155]. Furthermore, integrating separate PCPs
can lead to multi-functionality and synergetic or concerted
functionality. Some state-of-the-art examples of such sys-
tems include PCP-on-PCP film and PCP-composite systems
[60,156].
(2) Static ? Dynamic. A paradigm shift in gas adsorption/sepa-
ration has occurred with flexible and stimuli-responsive
PCPs [110]. Controlled switchable behaviour can occur by
applying light irradiation, an electric field, mechanical force,
a temperature change, or the presence of a particular spe-
cies. Artificial switching of the structure and conductivity
in PCPs may play an important role in future sensors or
safety-related devices.
(3) Isotropic ? Anisotropic. Unidirectional motion may allow
for possibilities not found in randomized counterparts. Con-
duction pathways through aligned pores or along stacked
heteroatoms/aromatic units allow for 1D bidirectional
motion. A stimulus applied to one side may allow collective
 J.-S.M. Lee et al. / Coordination Chemistry Reviews 421 (2020) 213447
Fig. 7. Methodologies for next-generation transportive PCPs.
motion toward the other side. This could also occur in a sta-
tic crystal with a gradient structure. If both sides of the crys-
tal possessed varying conduction potentials by means of
structural difference, unidirectionality could be envisioned.
(4) Order ? Disorder. The electronic properties of established
materials, such as silicon or Group III/V compounds, are
due to the presence of defects and trace chemical impurities
[157]. In PCPs, defect incorporation is known to enhance
sorption and catalytic applications, in addition to modifying
their physical properties [158]. Strategies could include lin-
ker and/or metal ion vacancies which affect transport path-
ways and give rise to electronic coupling states, charge input
via oxidation of the metal ions, or doping in the framework.
(5) 3D ? Low dimensionality. Ultrathin 2D PCPs have shown
particular promise in electric conductivity. They elevate
themselves above other 2D materials through their modular
designability. However, controlled and predictable synthesis
of 2D PCPs is still difficult to achieve. Further work is
required to understand the fundamental principles of
designing 2D PCPs with predictable structure–property rela-
tionships, such as through computational methods or exper-
imentally by tuning the electronics of the ligand (e.g., via p-
conjugation/heteroatom variation).
This perspective highlights some important developments and
strategies for introducing transport properties into PCPs. The tun-
able properties of PCPs—porosity, crystallinity, functionality,
dynamics, and stability—provide a promising platform on which
to develop these materials for applications to overcome the prob-
9
lems of existing technologies. Although one may assume that we
should strive toward higher transport properties to yield better
performance, it is important, if not more important, to develop
practical materials for real applications. The realization of new
methods and a specific train of thought are important for the
expansion of this field and to set PCPs apart from currently leading
materials.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work is supported by the ERATO and ACCEL project of the
Japan Science and Technology Agency (JST) and KAKENHI Grant-in-
Aid for Specially Promoted Research (No. 25000007) and Scientific
Research (S) (JP18H05262) from the Japan Society of the Promotion
of Science (JSPS). KO acknowledges KAKENHI Grant-in-Aid for
Early-Career Scientists (JP19K15584) for financial support.
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