Synthesis of oligodiacetylene derivatives from flexible porous coordination frameworks

Article abstract of DOI:10.1021/jacs.7b07699

Oligodiacetylenes (ODAs) with alternating ene-yne conjugated structure are significant materials for optical and electronic properties. Due to the low solubility of ODAs in common solvents, the synthetic approaches are limited. Here we disclose a new synthetic approach of ODAs without a side alkyl chain using a porous coordination polymer (PCP) as a sacrificial template. 1,2-Bis(4-pyridyl)butadiyne, which works as a monomer, was embedded in the flexible framework of the PCP, and ODAs were synthesized via utilization of the anisotropic thermal expansion of the PCP crystal. The oligomeric state of ODAs depends on the metal ion and coligand of the precursor.

Full text of DOI:10.1021/jacs.7b07699

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Article
Synthesis of Oligodiacetylene Derivatives from
Flexible Porous Coordination Frameworks
Yu-ichi Fujiwara, Kentaro Kadota, Sanjog S. Nagarkar,
Prof. Norio Tobori, Susumu Kitagawa, and Satoshi Horike
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b07699 • Publication Date (Web): 16 Sep 2017
Downloaded from http://pubs.acs.org on September 16, 2017
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Synthesis of Oligodiacetylene Derivatives from Flexible Porous
Coordination Frameworks
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†,‡
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†
,||
Yu-ichi Fujiwara, Kentaro Kadota, Sanjog S. Nagarkar, Norio Tobori, Susumu Kitagawa,*
,‡,||,#
and Satoshi Horike*
†
Functional Materials Science Research Laboratories, Research & Development Headquarters, Lion Corporation, 2-1,
Hirai 7-chome, Edogawa-ku, Tokyo 132-0035, Japan.
‡
§
Department of Synthetic Chemistry and Biological Chemistry, and Department of Molecular Engineering, Gradu-
ate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
||
#
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Institute for Advanced Study, and AIST-Kyoto Uni-
versity Chemical Energy Materials Open Innovation Laboratory (ChEM-OIL), Kyoto University, Yoshida, Sakyo-ku,
Kyoto 606-8501, Japan.
Oligodiacetylene, Porous Coordination Polymer, Thermal Expansion, and Cross Linking
ABSTRACT: Oligodiacetylenes (ODAs) with alternating ene-yne conjugated structure is one of the significant materials
for optical and electronic properties. Due to the low solubility of ODAs in common solvents, the synthetic approaches are
limited. Here we disclose a new synthetic approach of ODAs without side alkyl chain using porous coordination polymer
(
PCP) as a sacrificial template. 1,2-bis(4-pyridyl)butadiyne which work as a monomer were embedded in the flexible
framework of PCP, and ODAs were synthesized via utilization of the anisotropic thermal expansion (ATE) of PCP crystal.
The oligomeric state of ODAs depends on the metal ion and co-ligand of the precursor.
8
frameworks (MOFs) as sacrificial precursor. They are also
useful platform for the molecular synthesis. Sequential
INTRODUCTION
Since Wegner discovered the 1,4-diacetylene polymeri-
zation in solid state via topochemical reaction, polydi-
dimerization via the [2+2] cycloaddition, [2+2+2] cyclot-
rimerization, and the formation of an anhydride bridge
between free carboxylic groups are the examples. These
1
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acetylenes have been studied extensively owing to the
2
unique alternating ene-yne conjugated structure. In this
topochemical reactions were conducted by use of the ro-
bust crystal structure of PCP/MOFs, and this is not appli-
cable for the various oligomer formations. This is because
of the difficulty for the preparation of such topotactic
reaction environment for oligomers. Development of the
synthetic route of organic oligomers such as ODA without
side alkyl chain by use of PCP/MOFs is therefore of gen-
eral importance and challenge. For the synthesis of oli-
gomer, we focused on the anisotropic thermal expansion
research field, control of the molecular structure is im-
portant for design of the optical and electronic
3
properties. Oligodiacetylenes (ODAs) with the well-
defined conjugated structure has also been the significant
4
synthesis target. Engineered crystalline hosts with hy-
drogen- or halogen-bonding are useful host for polydi-
5
acetylene synthesis, whereas ODAs with low polymeriza-
tion degree are typically synthesized by using So-
4
b,4c,6
nogashira−Glaser coupling reaction
or co-micellar
(
ATE) of the flexible PCP/MOFs derived from vibration of
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strategy . One of the issues with the sequential synthetic
approaches is the difficulty to synthesize the structures
without alkyl side chain due to the low solubility in or-
ganic solvents. Those alkyl chain sacrifices good conduc-
tive properties derived from the conjugated structure.
Therefore new routes are demanded for the synthesis of
ODAs without alkyl side chain.
the ligands and the metal nodes. Topochemical oligomer
synthesis requires the appropriate positioning of several
monomers in the crystal structure. The ATE property of
PCP/MOF would provide such a situation at a certain
temperature as shown in Scheme 1. Here, we demon-
strated the synthesis of various ODAs without alkyl side
chain by use of the PCP/MOFs having two dimensional
(2D) structures.
1
1
In recent years, remarkable numbers of the preparation
of functional solids such as porous carbon, metal nano-
particle, and organic polymer are reported by use of po-
rous coordination polymers (PCPs) or metal organic
Scheme 1. Schematic illustration of the oligomer syn-
thesis via ATE property of PCP/MOFs.
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sembled structure, where the gray, blue, red, and green col-
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ors denote C, N, O, and Zn, respectively, and H atoms are
omitted.
Existence of guest DMF in crystal structure was con-
1
firmed by H NMR and thermogravimetric analysis (TGA).
In the crystal structure, the guest DMF molecules are dis-
ordered even at −120 °C, therefore the positions of the
guest molecules are not determined. Degas treatment of
the single crystal of ZnCID-24 with guest gave the crystal
structure of guest-free ZnCID-24. The crystal structure
shows only a small difference of the assembled structure
when compared to the ZnCID-24 with guest, and there-
fore the ZnCID-24 is regarded as a robust structure upon
the guest adsorption/desorption (Table S2).
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RESULTS AND DISCUSSION
We synthesized a bipyridyl ligand having butadiyne
unit for the monomer as shown in Scheme S1. We denote
it as bpb (bpb = 1,2-bis(4-pyridyl)butadiyne). We first in-
vestigated the oligomerization of bpb under conventional
route such as UV irradiation and thermal treatment.
However we recovered bpb, which means the oligomeri-
zation does not proceed in either route. We next synthe-
In order to investigate the thermal expansion property
of the ZnCID-24, we performed variable temperature sin-
gle crystal X-ray diffraction analysis over the temperature
range of between −120 and 26 °C.
sized a 2D interdigitated framework, [Zn(ip)(bpb)] which
n
is denoted as ZnCID-24 (CID = coordination polymer with
interdigitated structure, ip = isophthalate), as a template
for preparation of ODAs. The crystal structure of ZnCID-
24, which was determined by single crystal X-ray diffrac-
2+
tion analysis at −120 °C, is shown in Figure 1. Each Zn is
in a distorted octahedral geometry, being coordinated by
two nitrogen atoms of the bpb at the axial positions, two
oxygen atoms from the chelating carboxylate groups of
2+
the ip in the equatorial plane. The Zn and ip form a one
dimensional (1D) double chain structures along the b axis
and the further linkages of those chains via the bpb in the
axial positions generate a two dimensional structure (Fig-
ure 1a, 1b). The 2D structures are interdigitated mutually
to create a stable three dimensional (3D) assembled archi-
tecture from π−π interactions between the aryl planes of
the ip (bond distance = 3.7 Å) (Figure 1c).
Figure 2. ZnCID-24; (a) Temperature-dependence unit cell
parameters from −120 °C values determined by single crystal
XRD for a (red) and b (blue) axis, c axis (black). (b) PXRD
patterns from 25 to 300 °C. (c) Temperature-dependence unit
cell parameters determined by PXRD for c axis. (d) TG/DTA
profile.
As shown in Figure 2a, unit cell of the ZnCID-24 shows
anisotropic thermal expansion (ATE) behavior. Thermal
vibration of aryl plane of ip give the expansion along the b
axis, and negative expansion along the a axis is caused by
Figure 1. Crystal structure of ZnCID-24 showing: (a) 1D dou-
ble chain of [Zn(ip)] , (b) 2D layer structure, and (c) 3D as-
n
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slipping of the assemble layer derived from repulsion be-
tween aryl planes of ip. The expansion along the c axis is
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indicative of the dynamic nature of bpb and it exhibits the
highest expansion behavior. The coefficient of thermal
expansion (α) over the temperature of between −120 and
−
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−6
−6
2
6 °C are α = +44×10 , α = −20×10 and α = +110×10
a b c
−
1
K , respectively. The coefficient of thermal expansion
along the c axis is comparable to that of Nylon-6. We
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measured variable temperature powder X-ray diffraction
(
PXRD) of ZnCID-24 in the temperature range of 28−300
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°
C (Figure 2b). The reflection from the c axis shifts toward
lower angle of 2 theta, suggesting a gradual structural
transformation caused by the heating. The unit cell pa-
rameters of the c axis are calculated by the fitting analysis
of PXRD patterns. As shown in Figure 2c, the unit cell
parameters along the c axis in the ZnCID-24 exhibit even
more expansion behavior over the temperature range of
28−300 °C. The α parameter indicates higher thermal ex-
−
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−1
pansion behavior (+479×10 K ) compared with the tem-
perature range below 28 °C. Therefore the ZnCID-24 ex-
hibits specific thermal expansion behavior along the c
axis, where indicates the dynamic nature of bpb, accord-
ing to the heating.
We performed TGA coupled with the differential ther-
mal analysis (DTA) for the ZnCID-24 as shown in Figure
1
3
Figure 3. (a) C DDMAS spectra of ZnCID-24 (grey), H-
ZnCID-24 (black). (b) CO adsorption (solid circles) and de-
2d. TGA shows weight loss of 4% at 290 °C, and then
2
sorption (open circles) isotherms of ZnCID-24 (grey), H-
ZnCID-24 (black). (c) MALDI−TOF−MS spectrum of EH-
ZnCID-24. (d) Schematic view of cross linking behavior of
bpb in the ZnCID-24.
weight loss of 35% at the temperature of 380−450 °C.
1
From mass spectrometry and H NMR analyses, the first
weight loss (4% at 230−300 °C) for the ZnCID-24 is the
release of bpb, and the second weight loss suggests the
decomposition of ip and oligomeric bpb compounds (Fig-
ure S2). On the other hand, DTA exhibits a clear exo-
A single peak at 78 ppm corresponding to adjacent C−C
triple bonds in bpb is observed in the ZnCID-24, whereas
the H-ZnCID-24 does not have the peak, because all the
adjacent C−C triple bonds of bpb reacted as heating. The
peaks from the generated C−C triple and double bonds in
the H-ZnCID-24 are at the aromatic region of 110−160
ppm due to the change of bond environment. To observe
the porous structure of the framework after the thermal
thermic peak at 300 °C. Each H ip, bpb and analogous
2
interdigitated framework with 4, 4’-bipyridyl ligand,
11c
[
Zn(ip)(bpy)]n, does not show an exothermic peak as
heating (Figure S3). The exothermic event at 300 °C for
the ZnCID-24 implies cross-linking of bpb in the structure
due to the heating. For the cross linking of diacetylene
3
a
moiety, repeated distance of 4.9 Å are required. Accord-
ing to the thermal stimulation to the ZnCID-24, the dis-
tance between bpb get close to that distance, and then
cross linking reaction would proceed in the framework as
illustrated in Scheme 1.
treatment, we performed CO adsorption measurement of
2
the H-ZnCID-24 at −78 °C. The adsorption isotherm in
Figure 3b shows a gradual rise from the low relative pres-
sure region, which suggests the presence of microporous
structure. The adsorbed amount of CO in the H-ZnCID-
2
−1
2
4 is 42 mL g . On the other hand, although the ZnCID-
To elucidate the oligomer formation in the framework,
we conducted heat treatment of the ZnCID-24 at the
temperature of 320 °C, where it is above the temperature
of exhibits exothermic peak from TG/DTA profile. The
heated ZnCID-24 is denoted as H-ZnCID-24, where H
indicates heat treatment has completed. Elemental analy-
sis of the H-ZnCID-24 shows the component derived from
the releasing of bpb from the ZnCID-24 PXRD pattern of
the H-ZnCID-24 shows no significant diffraction peaks
because of the loss of crystallinity (Figure S4). We per-
2
4 also shows similar adsorption behavior, the adsorbed
−1
amount of CO is 33 mL g . The deference of adsorbed
2
amount between the H-ZnCID-24 and the ZnCID-24
would result from the increase of the adsorbed site of CO2
molecules due to the structure transformation of bpb.
We etched the H-ZnCID-24 with EDTA·4Na solution
(EDTA = ethylenediamine tetraacetic acid) to remove Zn
and ip. The etched sample is denoted as EH-ZnCID-24.
Matrix Assisted Laser Desorption Ionization-Time of
Flight-Mass (MALDI−TOF−MS) spectrum of the EH-
ZnCID-24 is shown in Figure 3c. The EH-ZnCID-24 shows
the repeated peaks of m/z = 204.1, which corresponds to
the molecular weight of bpb. On the other hand, the EH-
ZnCID-24 does not show the peak of m/z = 204.1 derived
from bpb monomer and dimer in the mass spectra below
13
formed solid state NMR measurements with C Dipolar
Decoupling Magic Angle Spinning (DDMAS) for the
ZnCID-24 and the H-ZnCID-24 (Figure 3a).
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m/z = 300 measured by APCI−MS (Figure S8g). As a fur- bpb along the b axis is 2.4 Å larger than that of the
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ther characterization, we conducted elemental analysis
for the EH-ZnCID-24, and the result matched with proto-
nated bpb oligomer (Table S1). Thus, it proves the cross
linking reaction of bpb in the ZnCID-24 occurs upon
heating to create the ODA without side alkyl chain as
shown in Figure 3d. Both ionization profiles of the MALDI
and the APCI suggest trimer is the dominant product for
this case. On the other hand, 20 unit oligomer as a maxi-
mum cross linking product is also observed. The oligomer
with long unit would be formed from small crystal parti-
cles, which are able to transfer the heat quickly.
ZnCID-24. We heated the ZnCID-25 at 320 °C for 15 min,
and then etched the heated sample by using EDTA·4Na
solution in the same manner with the case of the ZnCID-
24. As shown in Figure 4b, MALDI−TOF−MS spectrum of
the EH-ZnCID-25 shows the repeated peaks, and the tri-
mer formation are dominant. The results suggest that the
elongation of the b axis by applying ndc instead of ip in
the structure does not affect the formation of ODA and
they grow along the a axis, which is the inter-layer direc-
tion.
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We further investigated the effect of the metal ion in
the interdigitated PCP structure for the formation of
ODA. We synthesized different metal derivatives of the
ZnCID-24; CoCID-24 and CuCID-24. Both of the crystal
structures show analogous interdigitated motif, whereas
they exhibit the differences of bond distance and angle
(Table S2). Both of the TG/DTA profiles exhibit exother-
mic peaks attributed from the oligomerization at the
temperature of 330 °C and 260 °C, respectively (Figure
S14c, S14d). Accordingly, we characterized the oligomeri-
zation of the etched samples by MALDI−TOF−MS meas-
urements (Figure 5a).
We studied the mechanism of the preference trimer
formation. To investigate the effect of reaction tempera-
ture for the oligomerization behavior, we heated the
ZnCID-24 at the temperature of 200, 250, and 300 °C, and
characterized the oligomerization by APCI−MS measure-
ments (Figure S8d−f). The oligomer formation (trimer
dominant) is only observed for the reaction at 300 °C, and
the products prepared at 200 and 250 °C do not contain
any oligomer species. We next changed heating rate from
−1
−1
5
°C min to 1 and 15 °C min to study the influence of the
heating rate to the formation of oligomer. The products
−1
are same as those obtained from 5 °C min , and the oli-
gomerization is independent on the heating rate (Figure
1
S11). From the results H NMR, TGA−MS, and the reac-
tions under different temperatures or heating rates, the
cross linking happens due to ATE along the release of
partial bpb in the structure, and is under the thermody-
namic process.
In order to determine the growth direction of the oli-
gomer, we prepared other interdigitated framework with
naphthalene dicarboxylate instead of ip, [Zn(ndc)(bpb)]n
which is denoted as ZnCID-25 (Figure 4, ndc = naphtha-
lene 2,7-dicarboxylate).
Figure 5. (a) MALDI−TOF−MS spectra of the (left) EH-
CuCID-24 and (right) EH-CoCID-24. (b) Emission spectra of
EH-ZnCID-24 (black), EH-CoCID-24 (blue), EH-CuCID-24
Figure 4. (a) The 1D double chain of [Zn(ip)] from ZnCID-
n
24 and [Zn(ndc)]n from ZnCID-25. (b) MALDI−TOF−MS
(
red), and EH-ZnCID-25 (green) in water.
spectrum of EH-ZnCID-25.
Etched product from H-CoCID-24 (EH-CoCID-24) pro-
ZnCID-25 is constructed from 1D ribbon chains with an
vides mainly trimer molecules which is similar with that
of the EH-ZnCID-24, whereas the EH-CuCID-24 provides
dimer dominantly. The ATE property of PCP/MOFs are
influenced by the metal ions (Figure S1b and Figure S14c,
2+
eight-membered ring of Zn , two ndc moieties, and bpb
2+
coordinating to Zn , which forms the 2D layers, and the
layers are also interdigitated to create a 3D assembled
structure. As shown in Figure 4a, the distance of between
13
S14d), and the observed distinct formation of ODAs
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Single Crystal X-ray Diffraction Analyses. Single
would be derived from the different ATE property of each
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interdigitated structure. The extent of cross-linking pro-
cess in ODAs was monitored by recording emission pro-
file of etched products. As shown in Figure 5b, the EH-
CuCID-24, in which dimer formation is dominant, exhib-
its the emission band at 420 nm. On the other hand, the
emission band of the EH-ZnCID-24, the EH-CoCID-24
and the EH-ZnCID-25, in which trimer formation are
dominant, red shifted around 570 nm suggesting in-
creased conjugation. These fluorescence properties also
crystal X-ray diffraction measurements were performed
with a Rigaku AFC10 diffractometer with Rigaku Saturn
Kappa CCD system equipped with a MicroMax-007
HF/VariMax rotating-anode X-ray generator with confo-
cal monochromated MoKα radiation. The structures were
solved by a direct method (SHELXT-2014) and refined by
full-matrix least-squares procedures on F2 for all reflec-
tions (SHELXL-2017). The hydrogen atoms were posi-
tioned geometry and refined using a riding model. In the
crystal structures of ZnCID-24, CuCID-24, and CoCID-24,
guest DMF is highly disordered and the SQUEEZE func-
tion of PLATON were used to eliminate the contribution
of the electron density in the solvent region from the in-
tensity data, and the solvent-free model was employed for
the final refinement. For the refinement of the crystal
structure of ZnCID-24, we removed 97 electrons by using
SQUEEZE command. This corresponds to one DMF
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support the emission behavior from the oligomer state.
CONCLUSION
In this work, we employed ATE property of the flexible
PCP/MOFs for the topochemical synthesis of ODAs with-
out alkyl side chain. ZnCID-24 having 2D structure ex-
pands the crystallographic unit cell along the c axis due to
the heating. It is accompanied with the releasing of bpb,
and then bpb forms oligomer in the framework at the
temperature above 300 °C. The oligomeric unit of the
products depend on the metal ions in frameworks, where
1
which was confirmed by H NMR, and TGA. We estimated
the percentage of solvent accessible voids (SAVs) by using
PLATON software and these are 32 % for guest-free
2+
2+
2+
14
Zn and Co show trimer formation and Cu shows di-
mer formation dominantly. The ATE property is often
observed in PCP/MOFs, but no attempt is reported for
the synthesis of functional molecules so far. The proposed
approach in this work would inspire the new route of syn-
thesizing of various functional oligomers.
ZnCID24.
General Methods. Variable temperature PXRD data
were collected on a Rigaku SmartLab multi-purpose dif-
fractometer (Cu Kα radiation) equipped with temperature
changer attachment. The unit cell parameters of a, b, and
c axis were calculated by the fitting analysis of PXRD pat-
terns using PDXL software from Rigaku. TG/DTA was
EXPERIMENTAL SECTION
performed using a Rigaku Thermo plus TG 8120 at the
°
Synthesis of ZnCID-24. Zn(NO ) ·6H O (298 mg, 1.0
temperature range from 30 to 500 C under N gas flowing
3
2
2
2
°
−1
mmol), isophthalic acid (166 mg, 1.0 mmol), bpb (204 mg,
.0 mmol), DMF (40 mL), and MeOH (10 mL) were added
atmosphere with the ramping rate of 5 C min . TG−MS
was performed with a Rigaku Thermo plus EVO II
equipped with ThermoMass Photo/S by using electron
impact ionization method. FT−IR were performed with
1
to a 150 mL screw glass vial, then heated at 80 °C for 24 h.
Pale yellow crystals thus produced were washed with
DMF (50 mL × 2) and MeOH (20 mL × 1). In order to re-
move the guest solvent, the crystals were immersed in
deoxidized MeOH (50 mL) for overnight, and then de-
gassed under vacuum at 80 °C for 12 h. Synthetic proce-
dures of ZnCID-25, CuCID24, and CoCID-24 were men-
tioned in the supporting information.
1
Thermo Fisher Scientific Nicolet iS5. Liquid H NMR spec-
1
3
tra were recorded on a JEOL JNM-ECS400. Solid-state C
DDMAS NMR spectra were recorded on a Bruker Biospin,
ADVANCE III 400 NMR spectrometer. The spinning rate
for DDMAS spectra was 12 kHz. MALDI−TOF−MS were
performed with Bruker Daltonics ultraflex. As a matrix
molecule, we used 2,5-dihydroxybenzoic acid. APCI−MS
were performed with Thermo Fisher Scientific
Heat treatment of CID-derivatives. Degassed sample
(
×
100 mg) was homogenously placed on a ceramic boat (16
12 × 80 mm), and then heated up to the targeted tem-
EXACTIVE. CO adsorption isotherms were measured at
2
°
°
−1
−
78 C by BELSORP−mini with dry ice and MeOH dewar.
perature with heating rate of 5 C min under a flow of
nitrogen (0.5 L min ). After the holding for 15 min at tar-
°
−1
PCP samples were activated by heating at 120 C under
−
2
reduced pressure (< 10 Pa) for 12 h prior to the meas-
urement. The excitation and emission spectra for the
etched compounds were measured using Horiba
FluoroLog-3 instrument.
get temperature, H-CID-derivative was obtained. As a
target temperature, ZnCID-24, ZnCID-25, CuCID-24, and
°
CoCID-24 were adopted at 320, 320, 290, and 380 C, re-
spectively.
Etching of H-CID-derivatives. EH-CID-derivatives
were prepared by etching of H-CID-derivative with 0.05
M EDTA solution. Typically, H-ZnCID-24 (30 mg) was
stirred in 0.05 M EDTA solution (5 mL) for overnight, and
then insoluble residue, which is EH-CID-derivative, was
washed repeatedly with distillation water (5 mL × 2) and
MeOH (5 mL × 1). For the MALDI-TOF-MS and the Fluo-
rescence measurements, EH-CID-derivative was further
dissolved in 3 M HCl solution, and then a solution was
evaporated.
ASSOCIATED CONTENT
Supporting Information. Experimental details and addi-
1
tional characterizations (PXRD, TG/DTA, TG−MS, FT−IR, H
NMR, CO adsorption, MALDI−TOF−MS, APCI−MS, fluores-
2
cence, and crystallographic data). Crystallographic data in
CIF format, CCDC reference numbers 1520515−152519. This
material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
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Journal of the American Chemical Society
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Corresponding Author
Z.; Li, X.; Sun, Q.; Cheng, N.; Lawes, S.; Sun, X., Energy Storage
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Mater. 2015, 2, 35. (f) Xia, W.; Mahmood, A.; Zou, R.; Xu, Q.,
Energy Environ. Sci. 2015, 8, 1837. (g) Sun, J.-K.; Xu, Q., Energy
Environ. Sci. 2014, 7, 2071. (h) Lux, L.; Williams, K.; Ma, S., Cryst.
Eng. Comm. 2015, 17, 10. (i) Uemura, T.; Yanai, N.; Kitagawa, S.,
Chem. Soc. Rev. 2009, 38, 1228. (j) Distefano, G.; Suzuki, H.;
Tsujimoto, M.; Isoda, S.; Bracco, S.; Comotti, A.; Sozzani, P.;
Uemura, T.; Kitagawa, S., Nat. Chem. 2013, 5, 335. (k) Furukawa,
Y.; Ishiwata, T.; Sugikawa, K.; Kokado, K.; Sada, K., Angew. Chem.
Int. Ed. 2012, 51, 10566. (l) Ishiwata, T.; Furukawa, Y.; Sugikawa,
K.; Kokado, K.; Sada, K., J. Am. Chem. Soc. 2013, 135, 5427. (m)
Allen, C. A.; Cohen, S. M., Inorg. Chem. 2014, 53, 7014.
*
*
horike@icems.kyoto-u.ac.jp
kitagawa@icems.kyoto-u.ac.jp
Author Contributions
The manuscript was written through contributions of all
authors.
Funding Sources
This work was supported by a Grant-in-Aid for Young Scien-
tists (A), and a Grant-in-Aid for Challenging Exploratory
Research from Japan Society for the Promotion of Science
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(9) (a) Medishetty, R.; Park, I.-H.; Lee, S. S.; Vittal, J. J., Chem.
(
JSPS), and “Molecular Technology” of Strategic International
Commun. 2016, 52, 3989. (b) Mir, M. H.; Koh, L. L.; Tan, G. K.;
Vittal, J. J., Angew. Chem. Int. Ed. 2010, 49, 390. (c) Sato, H.;
Matsuda, R.; Mir, M. H.; Kitagawa, S., Chem. Commun. 2012, 48,
Collaborative Research Program (SICORP) from the Japan
Science and Technology Agency (JST).
7919. (d) Hu, F.-L.; Wang, H.-F.; Guo, D.; Zhang, H.; Lang, J.-P.;
ACKNOWLEDGMENT
Beves, J. E., Chem. Commun. 2016, 52, 7990. (e) Park, I.-H.;
Chanthapally, A.; Zhang, Z.; Lee, S. S.; Zaworotko, M. J.; Vittal, J.
J., Angew. Chem. Int. Ed. 2014, 53, 414. (f) Park, I.-H.; Medishetty,
R.; Lee, H.-H.; Mulijanto, C. E.; Quah, H. S.; Lee, S. S.; Vittal, J. J.,
Angew. Chem. 2015, 127, 7421. (g) Ragon, F.; Campo, B.; Yang, Q.;
Martineau, C.; Wiersum, A. D.; Lago, A.; Guillerm, V.; Hemsley,
C.; Eubank, J. F.; Vishnuvarthan, M.; Taulelle, F.; Horcajada, P.;
Vimont, A.; Llewellyn, P. L.; Daturi, M.; Devautour-Vinot, S.;
Maurin, G.; Serre, C.; Devic, T.; Clet, G., J. Mater. Chem. A 2015, 3,
The authors are grateful to Ms. K. Nishimura for technical
assistance with the experiments of MALDI−TOF−MS and
APCI−MS.
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