Precise Modulation of the Breathing Behavior and Pore Surface in Zr-MOFs by Reversible Post-Synthetic Variable-Spacer Installation to Fine-Tune the Expansion Magnitude and Sorption Properties

Article abstract of DOI:10.1002/anie.201604023

To combine flexibility and modifiability towards a more controllable complexity of MOFs, a post-synthetic variable-spacer installation (PVSI) strategy is used to implement kinetic installation/ uninstallation of secondary ligands into/from a robust yet flexible proto-Zr-MOF. This PVSI process features precise positioning of spacers with different length, size, number, and functionality, enabling accurate fixation of successive breathing stages and fine-tuning of pore surface. It shows unprecedented synthetic tailorability to create complicated MOFs in a predictable way for property modification, for example, CO₂and R22 adsorption/separation, thermal/chemical stability, and extended breathing behavior.

Full text of DOI:10.1002/anie.201604023

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201604023
German Edition: DOI: 10.1002/ange.201604023
Metal–Organic Frameworks
Precise Modulation of the Breathing Behavior and Pore Surface in Zr-
MOFs by Reversible Post-Synthetic Variable-Spacer Installation to
Fine-Tune the Expansion Magnitude and Sorption Properties
Cheng-Xia Chen, Zhangwen Wei, Ji-Jun Jiang, Yan-Zhong Fan, Shao-Ping Zheng, Chen-
Chen Cao, Yu-Hao Li, Dieter Fenske, and Cheng-Yong Su*
Abstract: To combine flexibility and modifiability towards
a more controllable complexity of MOFs, a post-synthetic
variable-spacer installation (PVSI) strategy is used to imple-
ment kinetic installation/ uninstallation of secondary ligands
into/from a robust yet flexible proto-Zr-MOF. This PVSI
process features precise positioning of spacers with different
length, size, number, and functionality, enabling accurate
fixation of successive breathing stages and fine-tuning of
pore surface. It shows unprecedented synthetic tailorability to
create complicated MOFs in a predictable way for property
into MOFs through sequential post-synthetic ligand
[
8]
exchange, offering an alternative to the one-pot synthesis
[
9]
of MTV-MOFs (multivariate MOFs) to place multiple
components, thus avoiding random distribution and disor-
[
9b]
der. However, it is noticeable that these PSM routes are
mainly limited to post-modifications on the main framework
[
10]
of parent MOFs. Recently, Zhou et al.
established an
unique sequential linker installation (SLI) strategy to con-
struct MTV-MOFs with exact positioning of multiple linkers,
and insertion of secondary ligands for pore space partition
[
11]
modification, for example, CO and R22 adsorption/separa-
and locking has also been accomplished.
Nevertheless,
2
tion, thermal/chemical stability, and extended breathing behav-
ior.
these post-syntheses still demand size- and symmetry-match-
ing of inserted ligands with primary frameworks. Insertion of
variable secondary ligands into the parent MOFs remains
unexplored, which may be expected to create more sophis-
T
he booming progress in the field of metal–organic frame-
[
1]
works (MOFs) has taken advantage of versatile combinations
of organic and inorganic synthetic strategies, and in turn,
propelled synthetic chemistry into a new realm for precise
ticated materials.
Based on the above progress in synthetic chemistry, we
herein propose a stepwise yet kinetically reversible synthetic
approach, that is, post-synthetic variable-spacer installation
(PVSI) strategy as depicted in Scheme 1, which presents
unprecedented control and tuning capacity through precise
and pinpoint installation and uninstallation of different
spacers. Starting from a flexible proto-MOF [(Zr (m -O) -
[1]
control over multiplicity and complexity. The syntheses of
MOFs have featured generation of permanent porosity,
construction of flexible and dynamic frameworks, and has
now reached post-synthetic modification (PSM) capability.
[2]
[3]
[4]
Flexible MOFs have triggered great interest in soft porous
6
3
8
[
2a]
1
1
crystals
displaying dynamic response to the external
(H O) (L ) ]·(solvents) (LIFM-28, L = 2,2’-bis (trifluoro-
2 8 4
[
5]
stimuli, resulting in a breathing effect that is tunable at
the molecular level to induce more functionality. For example,
a systematic tuning of the framework flexibility and gas
sorption has been accomplished via combining a library of
methyl)-4,4’-biphenyldicarboxylate, LIFM = Lehn Institute
[6]
functionalized linkers as mixed-components. Nevertheless,
rational fine-tuning of responsiveness of flexible MOFs is still
[
6]
desired but challenging, and precise control of breathing
behavior and fixation of swelling magnitude at stepwise stages
have not been achieved to the best of our knowledge.
On the other hand, the PSM methods provide a powerful
way to modify and create new functionalities, which are often
[
4b,7]
unattainable by direct de novo synthesis.
Specifically, the
PSM approach is useful to introduce multiple functionalities
[*] C.-X. Chen, Z. W. Wei, J.-J. Jiang, Y.-Z. Fan, S.-P. Zheng, C.-C. Cao,
Y.-H. Li, Prof. D. Fenske, Prof. C.-Y. Su
MOE Laboratory of Bioinorganic and Synthetic Chemistry
Lehn Institute of Functional Materials
School of Chemistry and Chemical Engineering
Sun Yat-Sen University, Guangzhou 510275 (China)
E-mail: cesscy@mail.sysu.edu.cn
Scheme 1. Post-synthetic variable-spacer installation (PVSI) demon-
5
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201604023.
stration by spacer H L . Elastic deformation occurring in the c-axis is
2
controllable by spacers of different lengths. H atoms and CF groups
3
are omitted for clarity.
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of Functional Materials), insertion of predetermined spacers
of variable lengths and substituents at selected sites proceeds
facilely through single-crystal to single-crystal (SC-SC) trans-
formations under mild conditions. Therefore, this strategy is
applicable to both flexible and post-modifiable MOFs by
comprising framework dynamics and modifiable sites, offer-
ing an easy way to precisely modulate the breathing behavior
by fixing the swelling framework at variate stages to a large
extent, and simultaneously modifying the pore surface for
solutions, they recover to the original phase readily. This
structural transformation takes place in a SC-SC manner,
designated as the narrow-pore (LIFM-28np) and large-pore
(LIFM-28lp) forms. Taking advantage of this breathing effect,
we find that different spacers with varied lengths can be
installed or uninstalled through a reversible SC-SC way in
mild post-synthetic conditions, thus facilitating PVSI process
based on this dynamic proto-Zr-MOF.
Careful examination of the Zr -cluster in LIFM-28 reveals
6
improved fluorocarbons and CO adsorption and separation
capacity.
that 8 terminal waters are located in two types of crystallo-
graphically independent positions in orthogonal directions,
assigning to modifiable sites A and B (Scheme 1). Since the
Zr cluster lies on a 4 screw axis, four H O on sites A aligning
2
To implement the PVSI strategy for dynamic MOFs,
1
a linear ligand H L was designed, which bears two trifluor-
2
6
2
2
omethyl groups at 2,2’-positions to twist two phenylcarbox-
ylate moieties off a plane. This ligand configuration is
essential for construction of 8-connected bcu framework
on c-axis point to the center of smaller pores along a- and b-
axis (sites A in a- and b-direction are crystallographically
equivalent but rotated by 908 and slid by half a c vector), while
[
12]
based on Zr -cluster, and may endow the framework with
four H O on sites B aligning on the a- or b-axis point to the
6
2
[
6,13]
flexibility.
As expected, colorless crystals were obtained
center of larger pores along the c-axis. Therefore, the smaller
spacing between adjacent sites A can accommodate shorter
1
through solvothermal reaction of ZrCl and H L in N,N-
4
2
dimethylformamide (DMF) at 1208C, giving LIFM-28 as an
isostructure of PCN-700 with required network. The as-
linear dicarboxylate spacers to replace four H O, thus block-
ing a- and b-pores (Scheme 1; Supporting Information, Fig-
2
[10]
prepared LIFM-28 crystallizes in P4 /mmc group (Supporting
ure S5), while longer spacers fitting between two neighboring
2
[
10]
Information, Table S1), possessing a neutral framework with
sites B will partition c-pores into segmental domains. As
illustrated in Scheme 1, the dihedral angle of diphenyl linkers
facing c-axis is stretchable because they chelate three facial Zr
[
14]
most probably octahedral Zr O (H O) clusters bridged by
6
8
2
8
1
eight L ligands while leaving four pairs of terminal H O
2
groups at equatorial plane appropriate for further modifica-
tion (Scheme 1; Supporting Information, Figure S4). The
atoms on one face of octahedral Zr cluster, but that facing a-
axis is relatively rigid because of unbending fixation by three
6
crystal lattice presents two types of pores, smaller ones
meridional Zr atoms on a Zr octahedron. Consequently, the
6
2
(
atom-to-atom separation 7 ꢀ 13 and 7 ꢀ 6 ꢁ ) along the a- or
framework is able to self-adjust the spacing between sites A to
install spacers in the c-direction with variable length, mean-
while little altering the separation between sites B in the a-
and b-directions. In other words, the framework can breathe
in the c-direction while keeping the size of c-pores almost
unchanged. This unique structural attribute lays the founda-
tion of PVSI strategy, namely, applying installation on sites A
to enable elastic deformation along c-axis depending on the
size of the spacers, but preventing installation on sites B to
purposely remain c-pores for functional modification. PVSI
presents an alternative functionalization pathway evolving
2
b-axis (a- or b-pores), and larger ones (17 ꢀ 17, 10 ꢀ 10 ꢁ )
along the c-axis (c-pores). The CF functional groups point to
3
the interior of the channels to bring hydrophobic character
(
Supporting Information, Figure S4). A striking feature of
LIFM-28 is the breathing behavior driven by removal/uptake
[
5g,13]
of solvated water, which is rarely observed for Zr-MOFs.
Upon heating at 1008C, the crystals transform into a denser
phase with the pore size along a/b-axis dramatically reduced
from 7.2 to 3.6 ꢁ (Scheme 2; Supporting Information, Figur-
[
5f]
es S5,S6), showing negative thermal expansion.
When
[
10]
soaking the shrinked crystals in water or acid/basic aqueous
from SLI method in which two types of linkers with mutual
matching length have been successfully positioned in two
distinct pockets of prototype PCN-700 in a fixed-order
sequence. The SLI strategy is preferable for MTV-MOFs
with mixed linkers, but nevertheless blocking pores in all
directions. The PVSI strategy aims at control of flexibility and
selection of installation sites, and features: i) the enabling of
fine-tuning of framework swelling magnitude by insertion of
spacers of different length in the same direction; ii) leaving
free pores for practical utilizations such as gas adsorption;
iii) modifying the surface of the main empty pores via
installation of functional spacers bearing varied substituents;
and iv) enhancing thermal stability and BET specific surface.
It is worthy to note that PVSI modification actually changes
the topology of parent framework after spacer coordination;
however, such post-synthetic coordination is labile enough to
[
7,10]
undergo solvent-assisted ligand exchange,
probably owing
to the low activation energy for kinetic replacement of H O
by carboxylate spacers in neutral form without altering
overall charge of proto-MOF.
Scheme 2. Reversible breathing behavior of LIFM-28, and stepwise
installation/ uninstallation of spacers (L –L ) in an increasing
sequence of expansion magnitude.
2
2
6
2
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To check if the proto-MOF LIFM-28 is robust enough for
repeating and successive PVSI processes, the chemical
stability of LIFM-28 has been tested under harsh conditions.
PXRD indicates that the structure remains intact upon
immersion in boiling water and aqueous solutions at pH 1
and 12 at 1008C (Supporting Information, Figure S7). These
results confirm that the proto-LIFM-28 is highly stable to
maintain the framework against solution treatment (noting
that phase change always occurs from LIFM-28np to LIFM-
2
8lp in aqueous media, and vice versa under activation
conditions). Therefore, PVSI process has been fully tested
with continually elongating spacers covering a wide range.
The spacing between adjacent sites A (designating as dspacer) in
LIFM-28 is 3.6 ꢁ in its np-form, becoming 7.2 ꢁ in its lp-
form, while the spacing between neighboring sites B is 16.3 ꢁ.
As analyzed above, because the spacing between sites B is
rather rigid, so installation of spacer shorter than 16 ꢁ will
inevitably select sites A. Along this line, two shorter spacers,
Figure 1. Comparison of elastic deformation depending on the size of
spacer (dspacer), crystal expansion magnitude along c-axis (clength), and
specific volume (Vspecific volume) relative to LIFM-28np, and changes of
pore size along the c-axis.
2
3
H L and H L with d falling within the range between np-
2
2
spacer
4
form and lp-form of LIFM-28, and three longer spacers, H L ,
H L , and H L with dspacer significantly longer than the
2
2
5
6
change between np-form and lp-form of LIFM-28 into
2
2
spacing in LIFM-28lp, have been chosen for PVSI testing
Scheme 2). As an example, fresh LIFM-28lp crystals were
consideration, it is evident that two shorter spacers (H L
2
3
(
and H L ) leads to contraction with regard to the original
LIFM-28lp, while three longer spacers (H L , H L , and H L )
2
2
4
5
6
immersed in a DMF solution of H L at 758C for 24 h, leading
to formation of LIFM-29 incorporating a H L spacer with
L :L ratio of 2:1. This means four H O on neighboring sites A
2
2 2 2
2
result in expansion significantly surpassing the breathing
magnitude driven by water solvent. Such a modulation of
breathing effect by spacer installation is unprecedented and
impressive, especially the extra expansion beyond the ordi-
2
1
2
2
can be kinetically replaced by two immigrating spacers to
generate a topologically new framework. All other spacers
can undergo similar PVSI process to generate isoreticular
[
2a,3,5]
nary breathing behavior driven by external stimuli.
3
4
5
MOFs of LIFM-30 (H L ), LIFM-31 (H L ), LIFM-32 (H L ),
Moreover, installation of different spacers is a precise control
of the breathing behavior by fixing the swelling framework at
variate stages.
2
2
2
6
and LIFM-33 (H L ), with spacers positioned exactly between
2
sites A (Scheme 2). The structures of all single crystals
produced via PVSI have been determined (Supporting
Information, Figure S4, Table S1). Treatments of the spacer-
installed crystals with water or acid/basic aqueous solution
lead to uninstallation of the spacers (Supporting Information,
Figures S8–S12) to recover LIFM-28lp, except LIFM-33,
which is apt to collapse under basic conditions, probably
To testify the reversibility of the PVSI process, uninstal-
lation and reinstallation of the inserted spacers have also been
fully performed in the following sequence (Supporting
Information, Figures S26–S45): i) soaking the crystal of
LIFM-29–33 in water at room temperature for a certain
time (1 h to 3 days); ii) checking the phase and chemical
change of the soaked crystal with single-crystal X-ray
because of the NH group. The phase purity of PVSI products
2
1
19
has been verified by PXRD measurements (Supporting
diffraction, PXRD, and H and F NMR spectroscopy; and
1
19
1
Information, Figures S14–S18). H and F NMR spectral
analyses of the digested LIFM-29–33 in comparison with
iii) reinstalling the spacers verified by PXRD and H NMR.
As expected, the single-crystal and powder X-ray analyses
unambiguously confirm that the water-soaked crystals trans-
starting LIFM-28lp reveal that two spacers per Zr cluster are
6
1
19
installed in LIFM-29 and LIFM-33, while only one spacer is
installed in LIFM-30–32 (Supporting Information, Figur-
es S19–S25, Table S2), in agreement with the single-crystal
analysis results.
The elastic deformation effect induced by PVSI of
different spacers can be evaluated by the crystal expansion
magnitude along c-axis (clength), and the specific volume
derived from the unit cell volume (Vcell) and the number of
form back into LIFM-28lp. H and F NMR monitoring of
the digested samples of soaked and reinstalled crystals verify
that the inserted spacers in LIFM-29–33 are completely
removed or reinstalled. Further confirmation comes from gas
sorption examination of the activated crystals recovered from
LIFM-30 (Supporting Information, Figure S46). Its sorption
isotherms closely match the profile with the pristine LIFM-
28np, evidently indicative of full recovery of the porosity and
complete removal of spacers along reversible PVSI process.
These phenomena strongly suggest that PVSI is a kinetically
controlled process via labile coordination between the
formula per unit cell (Z) in the single crystal (Vspecific volume
Vcell/Z), taking the densest LIFM-28np as the reference
Figure 1). It is clear that, in comparison with the shortest
spacing between sites A in LIFM-28np, the spacer elongation
=
(
inserted spacers and Zr clusters, in contrast to conventional
6
2
6
from H L (186%) to H L (316%) causes crystal expansion
one-pot synthetic and post-synthetic approaches, facilitating
reversible installation/uninstallation of spacers and efficient
recycling of the proto-MOF. In this sense, a continuous cycle
starting from the most compressed LIFM-28np to the most
2
2
along c-axis from 123% to 159%, and swelling of the specific
volume from 119% to 136%. In contrast, the pore size in c-
direction only shrinks less than 10%. Taking the structural
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interacting/coordinative sites or hydrophobic/hydrophilic
effect into the porous framework. The position and number
of post-modified spacers can be predictably and accurately
determined; therefore, fine-tuning of the pore properties is
possible. In general, all MOFs show good thermal and
1
chemical stability owing to existence of F-functionalized L
[
15]
carboxylate ligand and oxophilic Zr -cluster. Thermogravi-
6
metric analyses indicate that the frameworks decompose
above 3008C, increasing variably depending on the intro-
duced spacers (Supporting Information, Figure S51). The
variable-temperature PXRD patterns of LIFM-28lp confirm
that the structural transformation to LIFM-28np occurs
around 1008C, and retains the crystallinity up to 2008C.
After PVSI of different spacers, the framework stability
increases significantly up to 3758C for LIFM-29, 4258C for
LIFM-30, and 3508C for LIFM-32, while remaining
unchanged for LIFM-31 and LIFM-33 (Supporting Informa-
tion, Figures S52–S57), indicative of best enhancement from
F-substituents. At higher temperature, severe broadening of
PXRD patterns indicates collapse of the porous framework.
Owing to labile spacer coordination, LIFM-29–33 are ther-
modynamically unstable and undergo uninstallation of kinetic
spacers in water and acidic/basic aqueous solutions (Support-
ing Information, Figures S8–S12), but remain stable after-
wards.
2
5
Figure 2. Top: Stepwise installation/uninstallation from H L to H L
2
2
mediated by reversible PVSI processes with LIFM-28lp crystals to
achieve different stages of breathing behaviors in a continuous way.
Bottom: Elastic deformation in six stages reflected by specific PXRD
peaks shift.
The N sorption was performed at 77 K for all MOFs,
2
which display typical type-I isotherms with BET surface area
2
À1
increasing from 940 in LIFM-28lp to 1588 m g in LIFM-33
(Supporting Information, Figures S58–S66, Table S3). The
expanded LIFM-32 (Figure 2 top, shown by the broken
arrow) through every stage fixed by spacers is feasible via
reversible mediation by LIFM-28lp (shown by equilibrium
arrows). Since the structural transformation between np- and
lp-forms of LIFM-28 is facially driven by water uptake, the
key steps rely on the robustness of LIFM-28lp to endure
successive PVSI processes with different spacers. Therefore,
pore volume, estimated at p/p = 0.97, also increases from 0.44
0
3
À1
to 0.76 cm g , while the pore sizes fall in a similar range
around 13 ꢁ. These results are expectable since insertion of
flat spacers into smaller a/b-pores should generally expand
the overall specific surface areas along the main c-pores.
Slight variation of BET surface area and pore volume is due
to distinct functionalization of spacer substituents. It is
impressive that the modified MOFs show much higher
adsorption capacity and selectivity for chlorodifuoromethane
2
5
an experiment is designed to install H L -H L step-by-step
2
2
with the same LIFM-28lp crystals. As shown in the Support-
ing Information, Figure S47, stepwise installation and unin-
stallation of these spacers has been successfully accomplished,
where each PVSI step involves a process of spacer insertion
and LIFM-28lp recovery, which is testified by PXRD
monitoring (Supporting Information, Figure S48). In this
way, fixation of the breathing behavior at six stages could
be established, and the crystal elastic deformation along c-
axis could be precisely determined by the values of dspacer and
clength mentioned above, and reflected on the movement of the
PXRD peaks containing non-zero Miller l-indice of a crystal
plane (Figure 2; Supporting Information, Figure S49). Fur-
thermore, the robustness of LIFM-28 against spacer insertion/
(R22) and CO (Supporting Information, Figures S67–S98,
2
Table S4). At zero coverage, the R22 isosteric heat Q ranges
st
À1
from 26 to 36 kJmol (Supporting Information, Figure S86).
The highest value is from LIFM-30 containing fluorinated
[15]
spacers, being comparable with the best values reported.
Moreover, excellent R22 adsorption selectivity over N has
2
been achieved by the modified MOFs. Ideal adsorption
solution theory (IAST) calculation reveals that the initial
selectivities of LIFM-29–33 falls in the range 170–279, which
is a significant improvement by a factor of 4–7 from 42 of
LIFM-28lp (Figures 3 left, Supporting Information, Figur-
es S87–S98, Table S4). For CO , introducing NH groups in
removal has been testified by ten cycles of reversible PVSI
2
2
5
processes with H L , indicating little crystal degrading occurs,
LIFM-33 remarkably enhance CO uptake capacity due to
2
2
À1
as seen from PXRD monitoring (Supporting Information,
Figure S50).
very high Qst of about 40 kJmol , followed by LIFM-32
bearing OH sites and then other modified MOFs (Supporting
Information, Figure S85, Table S4). Again, the CO /N
On the other hand, PVSI of different spacers into a- and b-
pores in LIFM-28lp will simultaneously modify the surface of
the purposely remained c-pores. Anchoring the thiophene
2
2
adsorption selectivities of the post-installed MOFs are
distinctly higher than that of LIFM-28lp (Figure 3 right),
reaching highest value of about 30 by LIFM-33.
In summary, we have demonstrated a post-synthestic
variable-spacer installation (PVSI) strategy based on a stable
2
3
ring in H L , tetrafluorophenyl motif in H L , naphthalene
2
2
4
5
aromatics in H L , hydroxy group in H L , and amino groups
in H L on the surface of c-pores may bring potential
2
2
6
2
4
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Figure 3. IAST calculative selectivity of R22/N (10:90, left) and CO /
N (15:85, right) at 273 K.
2
2
2
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6
structural transition between a narrow-pore (np) and a large-
pore (lp) phases driven by solvent water uptake. Through this
strategy, a series of multifuctional MOFs are generated via
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pinpoint replacement of the selected terminal H O molecules
2
on a Zr cluster by linear spacers with different lengths and
6
substituents. The PVSI process is kinetically reversible in mild
conditions, providing a versatile alternative to conventional
PSM and one-pot syntheses by enabling exact positioning of
length-variable spacers in the same location. Therefore,
assembly and disassembly of different spacers through PVSI
approach endows a facile way not only to precisely control the
breathing behavior by fixing the elastic deformation in
a stepwise manner beyond normal external stimuli, but also
to fine-tune the pore surface to improve gas sorption capacity
and separation ability, enlarge BET surface area, and stabilize
the overall framework.
[
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2012CB821701), the NSFC Projects (91222201, 21573291),
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the STP Project of Guangzhou (15020016), and the NSF of
Guangdong Province (S2013030013474).
Keywords: breathing effect · metal–organic frameworks ·
post-synthetic modification · R22 adsorption · spacer insertion
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Revised: June 4, 2016
Published online: && &&, &&&&
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Metal–Organic Frameworks
Bringing PSM into dynamic MOFs: Post-
synthetic modification (PSM) is used to
install/uninstall varied linkers into/from
a flexible Zr-MOF. This post-synthetic
variable-spacer installation (PVSI) strat-
egy is used to tune elastic deformation,
breathing behavior, and stabilization of
the framework in controllable and pre-
dictable way. Tuning the pore surface
leads to a larger surface area and
improved gas separation and adsorption
capacity.
C.-X. Chen, Z. W. Wei, J.-J. Jiang, Y.-Z. Fan,
S.-P. Zheng, C.-C. Cao, Y.-H. Li, D. Fenske,
C.-Y. Su*
&&&& — &&&&
Precise Modulation of the Breathing
Behavior and Pore Surface in Zr-MOFs by
Reversible Post-Synthetic Variable-Spacer
Installation to Fine-Tune the Expansion
Magnitude and Sorption Properties
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
These are not the final page numbers!