Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate-Opening at Methane Storage Pressures

Article abstract of DOI:10.1002/anie.201800820

Herein, we report that a new flexible coordination network, NiL₂ (L=4-(4-pyridyl)-biphenyl-4-carboxylic acid), with diamondoid topology switches between non-porous (closed) and several porous (open) phases at specific CO₂ and CH₄ pressures. These phases are manifested by multi-step low-pressure isotherms for CO₂ or a single-step high-pressure isotherm for CH₄. The potential methane working capacity of NiL₂ approaches that of compressed natural gas but at much lower pressures. The guest-induced phase transitions of NiL₂ were studied by single-crystal XRD, in situ variable pressure powder XRD, synchrotron powder XRD, pressure-gradient differential scanning calorimetry (P-DSC), and molecular modeling. The detailed structural information provides insight into the extreme flexibility of NiL₂. Specifically, the extended linker ligand, L, undergoes ligand contortion and interactions between interpenetrated networks or sorbate–sorbent interactions enable the observed switching.

Full text of DOI:10.1002/anie.201800820

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Accepted Article
Title: Reversible switching between highly porous and non-porous
phases of an interpenetrated diamondoid coordination network
that exhibits gate-opening at methane storage pressures
Authors: Michael Zaworotko, Qingyuan Yang, Prem Lama, Susan Sen,
Matteo Lusi, Kai Jie Chen, Wenyang Gao, Mohana Shivanna,
Tony Pham, Shinpei Kusaka, Nobuhiko Hosono, John Perry,
Shengqian Ma, Brian Space, Leonard Barbour, and Susumu
Kitagawa
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201800820
Angew. Chem. 10.1002/ange.201800820
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Reversible switching between highly porous and non-porous
phases of an interpenetrated diamondoid coordination network
that exhibits gate-opening at methane storage pressures
Qing-Yuan Yang,[a] Prem Lama,[b] Susan Sen,[c] Matteo Lusi,[a] Kai-Jie Chen,[a] Wen-Yang Gao,[d]
Mohana Shivanna,[a] Tony Pham,[d] Nobuhiko Hosono,[c] Shinpei Kusaka,[c] John J. Perry IV,[a]
Shengqian Ma,[d] Brian Space,[d] Leonard J. Barbour,[b] Susumu Kitagawa,[c] and Michael J.
Zaworotko*[a]
Abstract: Some porous materials can reversibly change their crystal
whereas type-I (Langmuir) adsorption isotherms (Scheme 1a)
structure in response to interfacial sorbate/sorbent interactions. Here, are characteristic of rigid microporous materials, flexible
we report that a new flexible coordination network, NiL2 (L = 4-(4-
Pyridyl)-biphenyl-4-carboxylic acid), with diamondoid, dia, topology
switches between non-porous (closed) and several porous (open)
phases at specific carbon dioxide (CO2) and methane (CH4)
pressures. These phases are manifested by multi-step low pressure
isotherms for CO2 or a single-stepped high pressure isotherm for
CH4. The potential methane working capacity of NiL2 approaches
that of compressed natural gas but at much lower pressures. The
guest induced phase transitions of NiL2 were studied by single-
crystal X-ray diffraction (SC-XRD), in-situ variable pressure powder
XRD (PXRD), synchrotron powder XRD (SXRD), pressure-gradient
differential scanning calorimetry (P-DSC) and molecular modeling.
The collection of detailed structural information facilitates insight into
microporous materials tend to exhibit ‘stepped’ or ‘S-shaped’
isotherm profiles caused by breathing[6a] or swelling.[6b] When
porous after activation the pressure at which the step occurs
coincides with a structural transformation between less open
and more open phases via gradual opening (Scheme 1b, type F-
I)[6a] or sudden opening (Scheme 1c, type F-II).[6c]
Transformation from a non-porous (closed) activated phase to a
porous (open) phase can also occur gradually (Scheme 1d, type
F-III) or suddenly (Scheme 1e, type F-IV).[7] Type F-IV isotherms
are desirable for pressure swing gas storage, including
adsorbed natural gas (ANG) storage.[7d] This is because type I,
F-I, F-II and F-III isotherms (Scheme 1a-1d) retain adsorbed gas
at low pressures, thereby reducing working capacity.
the extreme flexibility of NiL2. Specifically, the extended linker ligand, Unfortunately, whereas there are now ca. 100 flexible metal-
“X-ligand”, L, undergoes ligand contortion and interactions between
interpenetrated networks or sorbate-sorbent interactions enable the
observed switching between closed and open phases, respectively.
We consider NiL2 to be prototypal for a large family of related porous
materials.
organic materials, [5b] FMOMS, only 2 FMOMs[7c, 7d] exhibit F-IV
isotherms and high uptake (>250 cc/cc). Kaskel’s group reported
[7c]
[Ni2(2,6-ndc)2(dabco)], DUT-8(Ni),
and Co(bdp) (bdp2-=1,4-
Crystalline solids are generally regarded as being rigid. However,
porous materials such as zeolites[1] and porous coordination
networks[2a] can exhibit guest induced structural transformations
when exposed to appropriate stimuli. The degree of flexibility
exhibited by such materials can be extreme in porous
coordination networks, which are also known as porous
coordination polymers (PCPs),[2] metal-organic materials
(MOMs)[3] or metal-organic frameworks (MOFs).[4] Flexible
microporous
materials[5-9]
challenge
classical
sorption
classifications because they necessarily change their pore
geometry as a consequence of a structural change. For example,
[a]
Dr. Q. Y. Yang, Dr. M. Lusi, Dr. K. J. Chen, Mr. M. Shivanna, Dr. J.
J. Perry IV, Prof. Dr. M. J. Zaworotko
Department of Chemical Sciences, Bernal Institute,
University of Limerick
Limerick, Republic of Ireland.
E-mail: Michael.Zaworotko@ul.ie
[b]
[c]
[d]
Dr. P. Lama, Prof. Dr. L. J. Barbour
Department of Chemistry and Polymer Science, University of
Stellenbosch, Matieland 7602 (South Africa)
Dr. S. Sen, Dr. N. Hosono, Dr. S. Kusaka, Prof. Dr. S. Kitagawa
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto
University, Katsura, Nishikyo-ku, Kyoto 615-8530, Japan
Dr. W. Y. Gao, Dr. T. Pham, Prof. Dr. S. Ma, Prof. Dr. B. Space
Department of Chemistry, University of South Florida, 4202 East
Fowler Avenue, Tampa, Florida, USA
Scheme I. Proposed classification of isotherm profiles for flexible microporous
materials: Type I = rigid microporous material; Type F-I = flexible microporous
material (gradual opening from small pore to large pore); Type F-II = flexible
microporous material (sudden opening from small pore to larger pore); Type F-
III
= flexible microporous material (gradual opening from non-porous to
porous); Type F-IV = Flexible microporous material (sudden opening from non-
porous to porous). Type F-V depicts a shape memory effect l[9c, 9d] and is not
relevant herein.
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benzenedipyrazolate) was reported by Long’s group.[7d] The
1e). Such extreme structural transformations between closed
latter is of special interest because it undergoes a structural
and open phases are unusual. We are aware of only four
[6b, 7c, 7d, 8d]
phase transformation in response to CH4 pressures between 5-
previously reported FMOMs
that are known to exhibit
[7d]
35 atm.
Herein we introduce a new porous material that
such dramatic solvent or gas induced structural change (Table
S4). The purity of the c1 phase was confirmed by PXRD and
synchrotron X-ray powder diffraction (SXRD) experiments. The
SXRD pattern of X-dia-1-Ni-c1 exhibits a diagnostic peak at 2θ
= 5.58° ( = 0.8269 Å) (Figure 1g). Thermogravimetric analysis
of X-dia-1-Ni-c1 indicated no weight loss until decomposition at
330 °C (Figure S6). X-dia-1-Ni-c1 reverts to X-dia-1-Ni-a1 when
soaked in DMF or toluene at room temperature for 1 minute
(Figure S7).
exhibits a type F-IV isotherm and high uptake, NiL2 (L = 4-(4-
Pyridyl)-biphenyl-4-carboxylic acid).
Solvothermal reaction of 4-(4-Pyridyl)-biphenyl-4-carboxylic
acid (HL) (Figure 1a) with Ni(NO3)2⋅6H2O in DMF at 105 °C
afforded crystals of the expected[10] diamondoid (dia) network
NiL2, X-dia-1-Ni. L was prepared through serial Suzuki-Miyaura
coupling reactions (Figure S1). Single crystals of as-synthesized
X-dia-1-Ni, X-dia-1-Ni-a1, characterized by SC-XRD revealed
that it crystallizes in tetragonal space group I41cd with a = b =
24.2018(6) Å, c = 16.2670(8) Å, V = 9528.0(7) Å3. Ni2+ cations
are coordinated to four oxygen and two nitrogen atoms from four
ligands and serve as 4-connected nodes. X-dia-1-Ni-a1 is a 6-
fold interpenetrated dia net (Figure 1c), interpenetration being
enabled by adamantanoid cages with Ni⋅⋅⋅Ni edges of 17.2 Å.
The accessible void volume available in X- dia-1-Ni-a1 is 49 %
despite the high level of interpenetration thanks to rectangular
channels along the c axis (Figure 1d). The bulk purity of X-dia-1-
Ni-a1 was confirmed by PXRD experiments (Figure 1f).
Structural transformations of NiL2. X-dia-1-Ni-a1 underwent
single-crystal-to-single-crystal (SCSC) transformations after
exchange with CH2Cl2 or heating at 85 °C for 24 h to less open
phases, X-dia-1-Ni-a2 and X-dia-1-Ni-a3, respectively (Figure
S3). Whereas space group and connectivity are unchanged,
reductions in cell volume (9528 to 8637 to 7441 Å3, for a1-a3,
respectively), length of the a and b axis (24.20 to 22.17 to 19.95
Å for a1-a3, respectively) and solvent-accessible void volume
(49, 43 and 33 % for a1-a3, respectively) accompanied the
phase changes (Figure 1e and Figure S4). The adamantanoid
cages exhibit Ni-Ni-Ni angles of 90°/120°, 80°/126° and 71°/132°
for a1-a3, respectively. The breathing of the framework is
accompanied by changes in N-Ni-N / C-Ni-C bond angles;
93.0°/101.5°, 90.7°/101.4° and 88.0°/102.4° for a1-a3,
Multistep CO2 adsorption isotherm. CO2, with its large
quadrupolar moment (13.4 × 10-40 Cm2) and small kinetic
diameter (3.3 Å), was chosen to probe how pressure affects
switching between the open (a1-a3) and closed (c1) phases.
The low-pressure adsorption isotherm of X-dia-1-Ni for CO2 at
195 K exhibits multiple steps and the surface area of the least
dense phase is 1641 m2 g-1 by Langmuir fitting (Figure 2a).
There is strong hysteresis and clear steps are also present in
the desorption isotherm. We conducted in situ PXRD and
sorption coincident measurements[12] (Figure 2b) by placing X-
dia-1-Ni-c1 on a copper plate under high vacuum before
collecting PXRD data during CO2 adsorption and desorption.
The diagnostic low angle peak of the c1 phase (10.03o,  =
1.54178 Å) gradually diminished as the diagnostic peaks of a3
(8.94o) and a2 (7.93o) appeared, indicative of gate opening
(Figure S8). The steep CO2 uptake after 0.1 bar is consistent
with transformation from c1 to an open phase. The PXRD
pattern did not change markedly in the pressure range 0.2-0.4
bar, which is consistent with the plateau observed in the
adsorption isotherm. When CO2 pressure was increased to 0.42
bar, the diagnostic low angle peak of a1 (7.08o) appeared. The
steep CO2 uptake around 0.45 bar is consistent with a structural
change from a2 to a1 that is complete at 0.77 bar. The in situ
PXRD patterns on desorption indicate reversible structural
changes between open and closed phases (Figure S9). X-dia-1-
Ni exhibited no N2 uptake at 1 bar and 77 K (Figure 2a).[13]
respectively (Table S3).
changes; the dihedral angle formed by the benzoate plane and
the pyridine plane is perpendicular in a1 (89.4°) but parallel in a2, Simulations predict N2 adsorption for a1 (Figure 2a) and
L also undergoes conformational
(6.1°) and a3 (1.8°). The breathing effect can be monitored by
PXRD (Figure S5); lowest angle reflection (200) shifts from 2θ =
7.08° in a1 to 2θ = 8.94° in a3.
stepwise CO2 adsorption at 195 K (Figure S17). The four steps
in the 195 K CO2 sorption isotherm of X-dia-1-Ni can be
attributed to structural transformations as the framework
switches from c1 to a3 to a2 and, finally, to a1. That these
transformations occur in SCSC fashion enables characterization
of each phase in a manner that is atypical of FMOMs, which
tend to be poorly crystalline following breathing or swelling.[6b]
Methane storage performance of X-dia-1-Ni. Natural gas
(NG), is mainly comprised of CH4 and increasingly utilised for
vehicular applications thanks to its geological abundance and
low carbon footprint.[14] Current storage technologies typically
Heating the a1-a3 phases in vacuo results in a color change
from dark green to light green and SCXRD revealed that the
light green phase, X-dia-1-Ni-c1, is a non-porous dia net
(orthorhombic space group Pnn2). Crystal morphology changes
accompany the structural transformation (Figures 1f, 1g) as
monitored by thermal microscopy. The Ni2+ cations of X-dia-1-
Ni-c1 adopt octahedral coordination geometry and serve as 4-
connected nodes as in the open a1-a3 forms. The planarity of L
as quantified by the N(pyridyl)-phenyl-centroid-C(carboxylate)
angle is 174° in a1, 176° in a2, 177° in a3 and, remarkably, 155°
in c1 (Figure 1e). The Ni⋅⋅⋅Ni edges of the adamantanoid cages
decrease from 17.2 Å (a1) to 16.3 Å (c1). We attribute the
existence of X-dia-1-Ni-c1 to the ability of L to contort and
changes in the coordination geometry (Table S3). PLATON[11]
revealed that X-dia-1-Ni-c1 has only 2% solvent-accessible
volume. Overall, X-dia-1-Ni-a1 undergoes a contraction of pore
volume from 0.58 cm3g-1 to 0.01 cm3g-1 in X-dia-1-Ni-c1 (Figure
o
use cryogenic (liquefied NG at -161 C, LNG) or high-pressure
(compressed NG at 210-250 atm, CNG), conditions that are
fraught with hazards and high costs. Adsorbed NG (ANG) using
porous materials could mitigate these risks and costs. However,
whereas 20,000+ physisorbent materials exist (e.g. activated
carbons,[15a] zeolites,[15b] MOFs,[15c,15d] molecular crystals[15e]),
none yet offer volumetric working capacity that exceeds 200 v/v
as offered by CNG (> 200 atm) at ambient temperature.
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Figure 1. (a) Structure of 4-(4-pyridyl)-biphenyl-4-carboxylic acid (HL). (b) Adamantanoid cage in NiL2. (c) 6-fold interpenetrated dia nets in NiL2. (d) Rectangular
channels viewed along the c-axis. (e) Single crystal structures of the porous (a1, a2, a3) and non-porous (c1) phases of X-dia-1-Ni. (f) Crystal morphology and
PXRD pattern of a1. (g) Crystal morphology and synchrotron PXRD ( = 0.8262 Å) pattern of c1.
A recent computational study of 650,000 porous materials[16]
suggests that no current class of rigid physisorbent is likely to
exceed the working capacity of CNG. This is mainly because
rigid materials typically exhibit type-I adsorption isotherms
(Scheme 1a) and NG remains adsorbed at the typical
deliverable pressure of 3-5 atm. Therefore, flexible materials that
exhibit type F-IV isotherms as they switch between closed and
open phases could achieve high working capacity that has
eluded rigid sorbents (Scheme 1e). However, even before cost
and stability issues are addressed, in order to be competitive
with CNG, a flexible material must exhibit gate-opening above 5
atm and below storage pressure (e.g. 35 or 65 atm). In addition,
storage capacity must be >200 v/v at 35 or 65 atm to compete
with CNG. Unfortunately, most FMOMs transform between less
open (narrow pore) and more open (large pore) phases
(Scheme 1b, 1c). Indeed, we are aware of only 5 FMOMs[7b, 7d, 8a-
uptake before the step (Figure S21). In situ variable CH4
pressure PXRD studies were conducted at 298 K by loading
activated X-dia-1-Ni into a capillary and exposing the sample to
methane (Figure S11). The kinetics of X-dia-1-Ni are too slow to
observe phase changes the mixed metal variant (X-dia-1-
Ni0.89Co0.11) more readily shows phase changes under pressure
(Figure S12). X-dia-1-Ni0.89Co0.11 is isomorphous to X-dia-1-Ni
and was formed under the same conditions. Under vacuum, the
c1 phase of X-dia-1-Ni0.89Co0.11 is present whereas from 25 bar
to 50 bar the peaks of the a1 phase appear. At 50 bar, X-dia-1-
Ni0.89Co0.11 had fully transformed to its a1 phase. The a1 phase
fully converts to the c1 phase by around 5 bar. This phase
change was also studied by P-DSC.[17] An activated sample of
X-dia-1-Ni was placed in a DSC sample chamber and exposed
to CH4 in the pressure range 1-50 bar at 298K. An exothermic
peak at 25 bar is consistent with the phase change observed via
in situ PXRD. The total CH4 uptake of X-dia-1-Ni at 25 °C is 176
cm3 g-1 (150 cm3 cm−3) for adsorption at 35 bar and 222 cm3 g-1
(189 cm3 cm−3) at 65 bar. The potential working capacity, 147
cm3 cm-3 as calculated from adsorption isotherm between 35 bar
and 5 bar, approaches that of benchmark MOFs (Table S5).
However, hysteresis reduces the working capacity to 110 cm-3
(5-35 bar) and 149 cm3 cm-3 (5-65 bar) respectively. Approaches
to control hysteresis are being investigated.
8c]
that exhibit structure transformations between closed and
open phases with appropriate NG gate opening pressure (5-35
atm), and only one exhibits high saturated uptake when open
(Table S1).[7d] NiL2 is the second FMOM that meets these
criteria. CH4 adsorption isotherms measured at 298 K reveal that
X-dia-1-Ni adsorbs minimal CH4 below the phase change
pressure (20 bar) and then exhibits an abrupt uptake in
adsorption as switches to an open phase (Figure 3a). 285 K and
273 K CH4 isotherms also exhibit a step but with increased
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Figure 2. (a) Measured CO2 (195K) and N2 (77K) adsorption isotherms for
X-dia-1-Ni and simulated N2 (195 K) adsorption isotherm for a1. (b) In situ
variable pressure PXRD ( = 1.54178 Å) of X-dia-1-Ni at different CO2
adsorption/desorption loadings collected at 195K. Calculated PXRD
patterns are black. The PXRD patterns reveal that X-dia-1-Ni undergoes
structural transformations from c1 to a3, a2 and then a1. Structural
transformations from a1 to a2, a3 and c1 occur during desorption.
Figure 3. (a) Total CH4 uptake isotherm at 298 K for X-dia-1-Ni. (b) Pressure-
ramped DSC (CH4, 298 K) for X-dia-1-Ni. (c) The simulated CH4 adsorption
isotherms in the open (a1) and closed (c1) phases of X-dia-1-Ni at 298 K with
the experimental adsorption isotherm. (d) The modelled structure at CH4
saturation in the open phase of X-dia-1-Ni. (e) Switching between closed
(left) and open (right) phases of X-dia-1-Ni under CH4 pressure.
Mechanism of structural flexibility. The mechanism of
structural flexibility for FMOMs such as paddle-wheel based
pillared-layered frameworks[18] (the prototype for which is DMOF-
1[18a]), MIL-53,[5a, 6a] and trigonal prism based networks such as
MIL-88,[6b] are based upon hinge motion associated with
carboxylate coordination. Structural characterization of the
various phases of NiL2 indicate a mechanism that largely relies
upon ligand contortion. In addition, c1 is stabilized by
interactions between interpenetrated networks. We note that a
similar dia network formed by a shorter linker ligand, 4-(4-
pyridyl) benzoic acid, did not exhibit framework flexibility under
the same conditions.[10c] We attribute this to the lesser ability of
shorter ligands to undergo extreme contortions of the type
observed for L. Therefore, the key to the phase changes
observed for this prototypal X-dia network is the use of the
extended “X-ligand”, L. The single point energies of L in a1
(Figure 4c) and c1 (Figure 4a) were calculated at the MP2/aug-
cc-pVDZ level of theory.[19] The energy difference calculated
between the two conformations of the ligand is +165 kJ mol-
1(Figure 4b). Ligands that can contort during structural
transformation are rare[20] and no others are yet known to induce
framework switching between closed and open phase. Ligand
contortion and framework strain might be expected to lead to
poor recyclability and reduced performance.[8e] We indeed
observed increases in pre-step adsorption at 298K after four
sorption/desorption cycles (Figure S23b).
Figure 4. Crystal structures of the c1 (a) and a1 phases (c) of X-dia-1-Ni.
(b) Conformation of L in the c1 and a1 phases. (d) Changes of cell volume
of X-dia-1-Ni during CO2 sorption. (e) Changes of cell volume of X-dia-1-Ni
during CH4 sorption. (f) Values of density and pore volume during
transformation from X-dia-1-Ni-c1 to X-dia-1-Ni-a1.
X-dia-1-Ni is only the second high surface area FMOM that
exhibits CH4 induced reversible switching with a type F-IV
isotherm at pressures relevant for NG storage. Materials such as
X-dia-1-Ni therefore have the potential to address storage and
on-demand delivery of fuel gases by addressing both the
working capacity and heat transfer issues that plague rigid
sorbents. Perhaps most importantly, X-dia-1-Ni belongs to one
of the longest studied and broadest classes of MOMs[10a,21] and
is therefore likely to be prototypal for a platform of related
FMOMs that exhibit switching and type F-IV isotherms, but
under different conditions. The possibility of fine-tuning of
performance towards a particular gas under a particular set of
conditions should be evident from this work.
In summary, X-dia-1-Ni undergoes pressure and solvent
induced SCSC transformations between closed and open
phases. Four distinct phases of X-dia-1-Ni were isolated and
studied by SC-XRD, PXRD and SXRD to provide structural
insight into how ligand contortion can enable structural flexibility.
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Crystallographic data for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data Centre (CCDC
1426847-1426850).
Acknowledgements
This work was generously supported by Science Foundation Ireland (SFI
Award 13/RP/B2549). We thank K. Forrest for the simulations of
adsorption isotherms. L.B. thanks the National Research Foundation of
South Africa for financial support and PL thanks the Claude Leon
Foundation for a postdoctoral fellowship. B.S. acknowledges the National
Science Foundation (Award No. CHE-1152362), including support from
the Major Research Instrumentation Program (Award No. CHE-1531590),
the computational resources that were made available by a XSEDE
Grant (No. TG-DMR090028), and the use of the services provided by
Research Computing at the University of South Florida. N.H. and S.
Kitagawa acknowledge the financial support of KAKENHI, Grant-in-Aid
for Specially Promoted Research (No. 25000007) from the Japan Society
of the Promotion of Science (JSPS). S. Kusaka and S. Kitagawa are
thankful to the ACCEL program of Japan Science and Technology
Agency (JST) for the financial support. We thank Diamond Light Source
for access to beamline i11 (EE16167-1).
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Keywords: flexible microporous materials • switching • stepped
adsorption isotherm • contortion 4 • methane storage
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This article is protected by copyright. All rights reserved.

10.1002/anie.201800820
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
A new flexible coordination network,
NiL2 (L = 4-(4-Pyridyl)-biphenyl-4-
carboxylic acid), undergoes extreme
structural transformations, enabled by
ligand contortion, between non-porous
(closed) and porous (open) phases as
exemplified by stepped isotherm.
Qing-Yuan Yang, Prem Lama, Susan Sen,
Matteo Lusi, Kai-Jie Chen, Wen-Yang Gao,
Mohana Shivanna, Tony Pham, Nobuhiko
Hosono, Shinpei Kusaka, John J. Perry IV,
Shengqian Ma, Brian Space, Susumu
Kitagawa, Leonard J. Barbour, and Michael
J. Zaworotko*
Reversible switching between highly
porous and non-porous phases of an
interpenetrated diamondoid
coordination network that exhibits gate-
opening at methane storage pressures
This article is protected by copyright. All rights reserved.