Article

pubs.acs.org/IC

Porous Supramolecular Networks Constructed of One-Dimensional

Metal−Organic Chains: Carbon Dioxide and Iodine Capture
Fei Yu,† Dan-Dan Li,† Lin Cheng,‡ Zheng Yin,† Ming-Hua Zeng,*,† and Mohamedally Kurmoo§
†
Department of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Key Laboratory for the Chemistry and
Molecular Engineering of Medicinal Resources (Ministry of Education), 15 Yucai Road, Guilin 541004, P. R. China
‡
Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, School of Chemistry and Chemical Engineering, Southeast
University, Nanjing 211189, China
§
Institut de Chimie de Strasbourg, CNRS-UMR 7177, Université de Strasbourg, 4 Rue Blaise Pascal, 67008 Strasbourg Cedex, France
*
S Supporting Information

ABSTRACT: In search of porous materials for selective sorption and iodine

inclusion, we have found two networks made of chains with a kink at the
metal nodes held together by supramolecular interactions (H-bond and π···π
stacking). The solvent can be removed and replaced reversibly without loss of
crystallinity, as demonstrated by single-crystal-to-single-crystal crystallogra-
phy. In contrast, iodine uptake degrades the crystallinity to amorphous, and it
regains its crystalline state after removal of the iodine at 200 °C. Slight
differences in behavior of the sorption and inclusion properties between the
tetrahedral metal nodes, Zn and Co, are associated with the size of the nodes.
An important feature is the extent of iodine that can be included between the
chains that is doubled with temperature from 30 to 100 °C and exceeds the
weight in mass of the compounds.

■ INTRODUCTION
While major efforts are being devoted to metal−organic
framework for the storage of fuel gases for the future safe
and environmentally friendly use of hydrogen as our source of
energy,1 there is also some interest in the use of soft porous
crystals based on nonbonded chains or layers held by
supramolecular interactions.2,3 Interestingly, both systems
carry their advantages and disadvantages. The former class
has marginal variation of their void spaces through limited
allowable changes in bond distances and angles; thus, they are
fairly rigid in most cases and in many cases retain their
crystallinity upon modifications.4 However, the latter has much
more freedom of movement and can show a wider variety of
structural properties,2,5 viz., reversible single-crystal-to-single-
crystal (SC−SC), reversible single crystal to amorphous, and
also nonreversible transformations.6,7 The flexibility and
dynamics of the porous crystals have been studied on some
occasions. Such work became more prominent when Kitagawa
and colleagues prepared several of these systems and studied
their structural properties as well as their dynamics during gas
sorption.2a,5a They highlighted the great advantage of being able
to store more guests than in bonded frameworks.8 Examples
based on both chains and layers have been reported,9,10 though
from a design point of view the former is more easily
controlled. Thus, there are few more linear chains ones.
Like matches in a box, the structure and shape of the match
define the efficiency of the packing. When they are regular the
packing allows for no void space but when they are rugged or
irregular the packing is not so efficient, and voids are created in
between.9 In crystals, one can regard the ruggedness by the
presence of bulky groups protruding perpendicular to the chain
compounds. A good example of this case is Zn(isophthalate)
(derivatives of bipyridyine having different lengths) where the
bpy bridges the Zn and one of the carboxylate bridges the zinc
of an adjacent chain forming a ladder.11 Due to the protruding
benzenecarboxylate the efficient packing of the ladders is
hampered thus producing space between them. Such a strategy
was successfully extended to different lengths of bpy to
generate different sizes of cavities.12 Porosity has been observed
for structures with different packing motifs, including crisscross
and interdigitating of chains.3,13 Most important in the stability
of these structures is the supramolecular interactions, viz.,
hydrogen bonds and π−π overlaps.
As the most versatile part of the entities forming the chains is
the organic ligands used, much of the known works concentrate
on the use of linear spacer ligands coordinated to the metal ions
in a linear fashion.9,14 In our previous study, 1H-benzimidazole-
5-carbonate and its 2-site modified derivatives were widely used
to construct several 2D or 3D coordination polymers.15 In such
kinds of ligands, the imidazole can bind to one or two metal
ions based on the departure of 1-site hydrogen while the
carboxylate has numerous possibilities and the 2-site substituent
group can affect the final structure. Apparently, when the 1-site
hydrogen is maintained, the ligand can be viewed as curving
bridging spacer to construct 1D ribbon or zigzag chains.16
Received: November 3, 2014

© XXXX American Chemical Society A DOI: 10.1021/ic502650z

Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Especially, the packing of such irregular chains may result in
supramolecular structure with void space.3 On the basis of such
design, here we will present two solvated compounds,
{[Zn(ebic)2]·EtOH}n (1·EtOH) and {[Co(ebic)2]·H2O}n (2·
H2O) where Hebic = 2-ethyl-1H-benzo[d]imidazole-5-carbox-
ylic acid (Figure 1), which were obtained by solvothermal
Figure 1. (a) Molecular structure of Hebic. (b) The coordination
environment of M(II) center. (c) Perspective view of the 1D
[M(ebic)2]n chain.
technique. Importantly, the 1D chain formed has a kink
imposed by the tetrahedral metal center that impaired the
packing efficiency where the void space is taken up by the
ethanol and water. They display reversible SC−SC and single-
crystal to amorphous transformations, gas sorption, and most
importantly iodine inclusion and releasing properties, including
electrical conductivity.
This work complements the recent research by us4,17 and
others18 on the inclusion of iodine molecules in the channels of
porous crystalline materials in view of introducing polarizability
and conductivity as well as the storage of radioactive iodine that
is a major waste of the nuclear industries and its use in
medicine.
5°/min. Calculated PXRD patterns were generated using Mercury
3.0.10 Raman spectra were obtained using a Renishaw inVia Raman
microscope equipped with a 785 nm diode laser and a 1200 lines/mm
grating. The high-pressure gas sorption measurements were performed
using the Belsorp HP-60 high-pressure sorption system. The C, H, and
N microanalyses were carried out with a Vario Micro Cube elemental
analyzer. The FT-IR spectra were recorded from KBr pellets
containing ca. 0.5 mg of the compound in the range 4000−400
cm−1 on a PerkinElmer one FTIR spectrophotometer.
Synthesis of {[Zn(ebic)2]·EtOH}n (1·EtOH). A mixture of
Zn(NO3)2·6H2O (150 mg, 0.5 mmol) and Hebic (30 mg, 0.15
mmol) in EtOH (8 mL AR-grade ≥99.7%) was adjusted to pH = 7
with Et3N in a Teflon-lined stainless steel autoclave which was heated
at 140 °C for 3 days. After the autoclave has been cooled at a rate of 10
°C h−1 to 25 °C, the colorless square shaped crystals of 1·EtOH were
collected, washed with EtOH, and dried in air (yield: 25.7 mg, 35%
based on ligand Hebic). The phase purity of the bulk product was
confirmed by PXRD and elemental analyses (%) calculated for 1·
EtOH (C22H24N4O5Zn): C, 53.94; H, 4.94; N, 11.44. Found: C,
53.77; H, 4.89; N, 11.58. IR (KBr, cm−1): 3094 (w), 2980 (w), 1584
(s), 1478 (m), 1456 (m), 1384 (s), 1078 (w), 1034 (w), 818 (m), 782
(m).
Synthesis of {[Zn(ebic)2]}n (1). Compound 1 was obtained by
heating crystals of 1·EtOH under a dynamic vacuum at 150 °C for 12
h. The crystals remain colorless.
Synthesis of {[Co(ebic)2]·H2O}n (2·H2O). A mixture of Co-
(NO3)2·6H2O (291 mg, 1.0 mmol), Hebic (60 mg, 0.31 mmol), NaN3
(20 mg, 0.31 mmol), and H2O (8 mL) was sealed in a Teflon-lined
steel autoclave and heated at 170 °C for 3 days. After the autoclave has
been cooled at a rate of 10 °C h−1 to 25 °C, the blue prismatic shaped
crystals of 2·H2O were collected, washed with H2O, and dried in air
(yield: 45.2 mg, 32% based on ligand Hebic). The phase purity of the
bulk product was confirmed by PXRD and elemental analyses (%)
calculated for 2·H2O (C20H20N4O5Co): C, 51.73; H, 4.56; N, 12.06.
Found: C, 51.37; H, 4.85; N, 12.99. IR (KBr, cm−1): 3454 (w), 1610
(s), 1576 (vs), 1482 (s), 1380 (vs), 1074 (w), 1040 (w), 822 (m), 782
(s), 702 (m).
Synthesis of {[Co(ebic)2] }n (2). Compound 2 was obtained by

■
EXPERIMENTAL SECTION
Materials and Physical Measurements. Thermogravimetric
analyses (TGA) were performed on a SETARAM LABSYS evo
TGA instrument in flowing N2 at a heating rate of 5 °C per minute in
the range 25−800 °C. Powder X-ray diffraction (PXRD) intensities
were measured at 293 K on a Rigaku D/max-IIIA diffractometer (Cu
Kα, λ = 1.540 56 Å). The crystalline powder samples were prepared by
crushing the crystals and the PXRD scanned from 5 to 60° at a rate of
heating crystals of 2·H2O under dynamic vacuum at 150 °C for 12 h.
The crystals retain their purple color.
Synthesis of {[Zn(ebic)2]·xI2 }n (1⊃xI2) and {[Co(ebic)2]·x′I2}n
(2⊃x′I2). Crystals of 1 and 2 (100 mg) were, respectively, soaked in 20
mL of 0.1 mol L−1 cyclohexane solution of iodine for 8 days at
different temperatures. The values of x and x′ were confirmed by TG
and EA: x = 0.55, 0.65, 1.00, and 1.30 and x′ = 0.60, 0.70, 1.00, 1.30 for
the temperature of 30, 50, 80, and 100 °C, respectively. TG curves are
shown in Supporting Information Figure S6, and the calculated and
observed values are listed in Supporting Information Table S3. The

Table 1. Crystallographic Data and Structure Refinement

1·EtOH 1 2·H2O 2
formula C22H24N4O5Zn C20H18N4O4Zn C20H20CoN4O5 C20H18CoN4O4
fw 489.82 443.75 455.33 437.31
space group P21/n P21/n P21/n P21/n
a/Å 14.3310(2) 14.2994(3) 14.0279(3) 14.0754(5)
b/Å 8.2853(1) 8.0692(2) 8.1674(3) 8.1320(4)
c/Å 18.4066(4) 18.2695(5) 18.7317(5) 18.7324(8)
β/deg 90.173(2) 90.551(2) 94.300(2) 93.462(4)
V/Å3 2185.53(6) 2107.92(9) 2140.1(1) 2140.2(2)
Dc/g cm−3 1.489 1.398 1.413 1.357
Rint 0.031 0.021 0.025 0.043
R1a (I > 2θ) 0.037 0.046 0.050 0.058
wR2b (all data) 0.092 0.136 0.159 0.138
GOF 1.04 1.09 1.04 1.002
void % 19.1 16.7 15.3 15.2

a
R1 =Σ||Fo| − |Fc||/Σ|Fo|. bwR2 =[Σw(Fo2 − Fc2)2/Σw(Fo2)2]1/2.

B DOI: 10.1021/ic502650z
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
data of calculated and observed elemental analyses are given in
Supporting Information Table S4.
X-ray Crystallography. Single-crystal X-ray diffraction (XRD)
data collection for 1·EtOH was conducted on a Bruker SMART APEX
II CCD diffractometer, and data for 1, 2·H2O, and 2 were collected on
an Oxford supernova diffractometer (Mo, λ = 0.710 73 Å) by using the
θ−ω scan technique at 150 and 273 K, respectively. Data were
corrected for absorption using SADABS.19 The structures were solved
by direct methods and refined with a full-matrix least-squares
technique within the SHELXTL program package.20 All non-hydrogen
atoms were refined with anisotropic displacement parameters. The
hydrogen atoms were generated geometrically (C−H 0.96 Å), except
for parts of the solvent molecules. For all structures, the guest
molecules were determined by thermogravimetric analyses (TGA).
The crystal data and structure refinement results are listed in Table 1,
while the selected bond distances and bond angles are listed in
Supporting Information Table S1. The CCDC reference numbers are
1021011−1021014 for 1·EtOH, 1, 2·H2O, and 2, respectively. The
supplementary crystallographic data for these compounds can be
found in the Supporting Information or can be obtained free of charge
from the Cambridge Crystallographic Data Centre via http://www.
ccdc.cam.ac.uk/data_request/cif.
■ RESULTS AND DISCUSSION
Synthesis. As part of our approach to porous materials we
have focused on the solvothermal reactions of pyridyl and
imidazole carboxylates that are suitable polytopic ligands for the
formation of metal−organic frameworks. In the present
synthesis, the solvothermal reaction of Hebic with divalent
transition metal salts adopting tetrahedral coordination results
in the two reported compounds here. There is no difference for
reactions performed at 140 or 160 °C and for different ratio of
reactants, but the crystalline products were single phase in each
case. Replacing the Et3N base by NaN3 works as well to give
the same products. For the synthesis of 2·H2O the latter
appears to be more suitable, and it reduces the amount of
cobalt oxides.
Crystal Structures. Single-crystal X-ray crystallographic
studies revealed that 1·EtOH and 2·H2O are both three-
dimensional supramolecular networks, constructed by one-
dimensional [M(ebic)2]n linear chains via N−H···O hydrogen
bonds and π···π stacking interactions. In the crystallographic
asymmetric unit, there are one tetrahedral M(II) ion (Zn for 1·
EtOH and Co for 2·H2O), and one ebic and solvent molecule
(EtOH for 1·EtOH and H2O for 2·H2O) (Figure 1a). Each
tetrahedral M(II) ion is surrounded by two oxygen and two
nitrogen atoms from four individual ebic ligands with M−N
and M−O distances of 2.23(1) and 2.24(1) Å, respectively.
Meanwhile, each ebic ligand adopts a cis coordination mode to
link two adjacent M(II) ions via the nitrogen atom of
benzimidazolyl ring and one monodentate carboxylate oxygen
atom into 1D [M(ebic)2]n linear chains orienting along the a-
axis with the shortest intrachain M···M distances of 7.319(2) Å
for 1·EtOH and 7.305(1) Å for 2·H2O (Figure 1b). The 1D
chains can also be regarded as the aggregates of [2 + 2]
{M2(ebic)2} metallocycles or two 1D [M(ebic)]n chains by
sharing the M(II) centers, which shows the 1D [M(ebic)2]n
chain is rigid. Moreover, in the {M2(ebic)2} of 1·EtOH and 2·
H2O, the two ebic ligands are parallel to each other with the
distance of 0.383(3) and 0.600(1) Å, respectively, which favors
the formation of moderate π···π stacking interaction.
Interestingly, the adjacent {M2(ebic)2} species are almost
mutually perpendicular with the angles of 88.33(3)° and
87.96(2)° for 1·EtOH and 2·H2O, respectively, consequent to
the tetrahedral coordination. Thus, it helps to reduce efficiently
C DOI: 10.1021/ic502650z
Article
steric hindrance between {M2(ebic)2} and improve the stability
of the 1D [M(ebic)2]n chains.
The 1D chains are connected to each other into a 3D
supramolecular network (Figure 2a) via strong N−H···O
Figure 2. (a) Hydrogen bonding and π···π interactions between
adjacent chains for 1·EtOH. (b) 3D supramolecular network showing
the 1D channels in 1·EtOH.
hydrogen bonds21 between the benzimidazolyl imino groups
and the uncoordinated carboxylate oxygen atoms with the N···
O distances of 2.796(2) Å for 1·EtOH and 2.787(4) Å for 2·
H2O, and weak π···π stacking interactions22 between the
intralayer phenyl rings with the centroid−centroid separations
of 3.581(3) and 3.573(2) Å for 1·EtOH and 2·H2O,
respectively. It is noted that only the benzimidazolyl nitrogen
atom and the uncoordinated carboxylate oxygen atom on one
ebic ligand of each {M2(ebic)2} participate in the construction
of intralayer N−H···O hydrogen bonds, and the corresponding
imino group and carboxylate oxygen atom of the other ebic
ligand is nonbonded in the layer, which is used to form
interlayer N−H···O hydrogen bonds, resulting in the 3D
supramolecular network. The N···O distances of interlayer N−
H···O hydrogen bonds are 2.796(2) Å for 1·EtOH and
2.763(2) Å for 2·H2O. In the 3D networks of 1·EtOH and 2·
H2O, there are 1D channels along the crystallographic a axis,
which are filled with ethanol molecule for 1·EtOH and water
molecule for 2·H2O (Figure 2b). The solvent molecules are
stabilized in the channels by O−H···O hydrogen bonds
between the solvent molecules and the uncoordinated
carboxylate oxygen atoms with O···O distances of 2.895(1) Å
for 1·EtOH and 2.837(4) Å for 2·H2O. The π−π stacking are
3.58 Å for 1·EtOH and 3.54 Å for 2·H2O. The PLATON-
calculated void volumes (Vvoid) without guest molecules are
19.1% for 1·EtOH and 15.3% for 2·H2O,23 respectively.
Importantly, when the crystals of 1·EtOH and 2·H2O were
heated at 150 °C, two corresponding desolvated products 1 and
2 were obtained by the SC−SC transformation, which were
also confirmed by PXRD for the bulk. Single-crystal X-ray
structures of 1 and 2 show the same 3D networks, but the 1D
channels of 1·EtOH and 2·H2O were empty. Compared to the
structures of 1·EtOH and 2·H2O, those of 1 and 2 show slight
structural deformation and reduction of the estimated void
volume to 16.7% for 1 and 15.2% for 2.23 Structure overlay
showed the slight difference between the molecular orientations
within the structures (Figure 3).
Thermal Stability. The thermogravimetric analyses (TGA)
of 1·EtOH and 2·H 2 O were carried out under an N 2
atmosphere using a heating rate of 5 °C min−1. The loss of
the solvents and stability of the desolvated frameworks of the
two complexes are consistent with the crystallographic
observations (Supporting Information Figure S1). For 1·
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 3. Views of overlaying structures of 1·EtOH (green) and 1
(pink), and of 2·H2O (red) and 2 (blue).
EtOH, the initial weight loss of 9.4% from 35 to 200 °C
indicates the removal of the ethanol molecules from the
channels (calcd 9.4%). Then, the structure without the solvent
molecules is maintained until 410 °C. The weight loss of 71.6%
in the range 410−800 °C corresponds to the decomposition to
ZnO (calcd 73.9%). For 2·H2O, there are two steps of weight
losses. The first one from 35 to 268 °C corresponds to the loss
of the water molecules. The observed weight loss of 4.0% is in
agreement with the calculated value of 4.0%. Then, the
desolvated network is also stable until 410 °C. The second
weight loss of 79.4% (calcd for CoO 79.6%) from 410 to 800
°C corresponds to the decomposition of the framework.
Powder X-ray Diffraction and Raman Spectroscopy.
PXRD studies have been used to check the purity of the
samples and also to study the structural changes that take place
during the modification. First, the experimental PXRD of 1·
EtOH and 2·H2O are the same as those calculated using the
single-crystal results (Figure 4 and Supporting Information
Figure 4. PXRD patterns of simulated from X-ray single crystal data
and observed from polycrystalline freshly synthesized 1·EtOH,
desolvated 1, 1⊃0.55I2, and its crystalline state after removal of I2.
Figure S2). After removing the solvents, the PXRD data of 1
and 2 are also similar to those calculated using the single-crystal
results. The temperature dependence of the SC−SC trans-
formations of 1·EtOH to 1, and 2·H2O to 2, were studied in
situ, which are found to be smooth with retention of the
crystallinity.
The Raman spectra of 1·EtOH and 1, 2·H2O, and 2 display
similar peaks and energies (Figure 5, Supporting Information
Figure S3). The almost unchanged peaks in the range 1500−
800 cm−1 are assigned to aromatic-ring stretching and in-plane
symmetric C−H stretching vibrations of benzimidazolyl ring of
D DOI: 10.1021/ic502650z
Article
Figure 5. Raman spectra of the ligand Hebic, 1·EtOH, 1⊃0.55I2, and
its crystalline state after removal of I2.
the ligand.24 The peak at 1656 cm−1 can be attributed to the
carboxylate vibration.
Selective Sorption of Guest Molecules. The micro-
porous characteristic of 1 and 2 may make the channels have
the selectivity for guest molecules with different size and shape.
Here, the desolvated 1 and 2 were immersed in different
solvents (H2O, EtOH, MeOH, CH2Cl2, Me2CO, C6H12) for 3
days, and then the TGA measurements show that the molecular
formulas after full sorption are 1·1.2H2O, 1·0.9EtOH, 1·
0.6MeOH, 1·0.6CH2Cl2, 1·0.4Me2CO, and 1·0.01C6H12 as well
as 2·1.1H2O, 2·0.8EtOH, 2·0.6MeOH, 2·0.6CH2Cl2, 2·
0.4Me2CO, and 2·0.02 C6H12 (Supporting Information Figure
S4). We may conclude that the small molecules (H2O, EtOH,
MeOH, and CH2Cl2) can easily enter the channels, but it is
difficult for large molecules (C6H12).2,3
Gas Sorption and Iodine Absorption. The permanent
porosities 1 and 2 demonstrated by CO2 sorption studies
(Langmuir surface area: 50 m2 g−1 (calcd 68 m2 g−1) for 1 and
42 m2 g−1 (calcd 63 m2 g−1) for 2, Figure 6) suggest they may
Figure 6. High-pressure CO2 sorption isotherms at 298 K for 1 and 2.
be suitable as hosts for absorbing iodine molecules.25 When
fresh samples of 1 (100 mg) were immersed in a cyclohexane
(5 mL) solution of I2 (0.03 mol L−1), the color of the crystals
changes from colorless to yellow, then brown, and finally black
(Figure 7a). When fresh samples of 2 (100 mg) were immersed
in the same concentration and volume of cyclohexane solution
of I2, the color of the crystals gradually changed from blue to
dark brown, and finally black (Figure 7b).
Although the single crystals after capturing I2 retained their
original well-defined external forms, the crystals diffract poorly,
and the resolution of the structure was not possible.17 PXRD
data (Supporting Information Figure S5) confirmed the
crystallinity of the host framework of the crystal and powder
samples of 1⊃xI2 and 2⊃x′I2. The Raman spectra of the I2-
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 7. Photographs showing the color changes when crystals of 1 (a) and 2 (b) were immersed in the cyclohexane solution of I2.
Figure 8. Kinetics of I2 delivery of 1⊃0.65 I2 (a) and 2⊃0.7 I2 (b) in methanol. The spectrum was recorded with interval of 2 min (5−21 min), 5 min
(21−61 min), and 10 min (61−181 min), respectively.
loaded samples show a large peak at 265 cm−1 corresponds to
the vibration of I2 in interaction with the networks. In order to
make clear how many I2 molecules fill the channels, PXRD, TG,
and EA of the samples of 1 and 2, soaked in the cyclohexane
solution of I2 at different temperatures (30, 50, 80, and 100
°C), have been measured. Most of the peaks in the PXRD of
1⊃xI2 remained at similar 2θ positions but were distinctly
weakened and broadened (Supporting Information Figure S5).
The change of intensity and width indicates that the resulting
solids 1⊃xI2 gradually lose their crystallinity as I2 molecules
diffused in. It is of note that most of the peaks of 2⊃x′I2 in the
PXRD are distinctly weakened, but when the I2 was removed
from the framework upon immersing the crystals in methanol
the peaks appeared again (Supporting Information Figure S5).
The unusual phenomenon can be explained by the high amount
of iodine in 1⊃xI2 that has a significant impact on the
crystallinity. Thus, PXRD of 1⊃xI2 and 2⊃x′I2 exhibited similar
patterns to those of 1 and 2, respectively.17
TG curves (Supporting Information Figure S6) and EA
measurements indicate that x = 0.55, 0.65, 1.00, and 1.30 and x′
= 0.60, 0.70, 1.00, 1.30 when the temperature is 30, 50, 80, and
100 °C, respectively. It is noticeable that the captured amounts
of I2 increase with temperature, which suggests that the
channels are flexible and enlarge with temperature (Supporting
Information Figure S7). Most importantly, when the temper-
ature is 100 °C, 1 and 2 can trap more I2 than that of the
maximally filled closely packed solid I2 in the corresponding
channels at room temperature (0.57 g/g). In comparison, the
uptake of I2 (0.31 and 0.35, 0.37 and 0.41, 0.56, and 0.57 g/g
for 1 and 2, respectively) at 30, 50, and 80 °C is remarkable and
comparable with zeolite 13X (0.32−0.38 g/g, with 10 Å pore),
and those (0.74 and 0.75 g/g for 1 and 2, respectively) at 100
°C are comparable with activated carbon (0.84 g/g) in the
E DOI: 10.1021/ic502650z
Article
cyclohexane solution of I2.26 It should be noted that the iodine
content is high to about 23.6−36.7% (wt %).
When the crystalline solids of 1⊃xI2 were soaked in
methanol for 10 min, the color of the solids changed from
black, to brown, then yellow to colorless, being an opposite
progress to captured I2, and the color of the methanol solution
deepened gradually from colorless to dark yellow, which
explained that the sorption and desorption of I2 are reversible.
Meanwhile, the desorption of I2 in 2 has also been observed by
the following experiments: 10 mg 1⊃0.65 I2 and a piece of KI
test paper were placed into a sealed vial together, and then KI
test paper gradually turned blue (Supporting Information
Figure S8).
To further investigate the kinetics of I2 delivery of 1⊃xI2 and
2⊃x′I2 in crystal transformation, UV−vis spectra were recorded
at room temperature as a function of time (Figure 8). The
absorbance of I2 in methanol increases linearly with time before
26 min for 1⊃xI2 and 2⊃x′I2, then it became slowly increasing
linearly with the time.17
Electrical Conductivity. Iodine is known to be an
interesting instant visual probe to study host−guest inter-
actions, and it can also introduce electrical conductivity. The
electrical conductivities of 1⊃0.55 I2 and 2⊃0.60 I2 are 3.47×
10−7 and 2.21 × 10−7 S/cm, respectively. They are nearly 80
and 90 times that for 1 and 2. Meanwhile, the values are lower
than that for solid I2 (7.69 × 10−6 S/cm) and much less than
for those MOFs with I2 loading (σ∥ = 3.42 × 10−3 and σ⊥= 1.65
× 10−4 S/cm),17 which may be attributed to the four close
parallel iodine chains are restricted within well-regulated
aromatic channels, inducing high efficiency of n → π*
charge-transfer (CT).27
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
■ CONCLUSION
Two porous supramolecular networks with 1D channels were
obtained from 1D rigid coordination polymers with hydrogen
bonding acceptors and donors, and conjugated aryl rings, which
are linked to each other by strong hydrogen bonds and π···π
stacking. The 1D channels of the 3D networks are filled with
solvent molecules. SC−SC transformation confirms the
channels are retained after the removal of the solvents. The
desolvated compounds exhibited fast and reversible iodine
uptake with visible color change, and the uptake increased with
temperature due to the channel expansion upon heating, which
demonstrates that these compounds are dynamic and exhibit
elastic guest accommodations. Iodine loaded crystals showed
80 times higher electrical conductivity compared to the guest
free ones; even the capsuled iodine was arranged with disorder
in the irregular channels.
■
ASSOCIATED CONTENT
*
S Supporting Information
Crystallographic data in CIF format, and additional plots and
data for the complexes in PDF format. This material is available
free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: zmh@mailbox.gxnu.edu.cn.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by NSFC (nos. 21371037,
91422302), Funds for Doctoral Discipline of University
(20134504110001), Guangxi Province Science Funds
(2012GXNSFFA060001, 2014GXNSFFA118003), Bagui
Scholar Program (2014A001), and Talents Highland of
Molecular Solid Materials of Guangxi Province in China.
M.K. is supported by CNRS-France.
■
REFERENCES
(1) (a) Rowsell, J. L. C.; Yaghi, O. M. Angew., Chem., Int. Ed. 2005,
44, 4670−4679. (b) Murray, L. J.; Dincă, M.; Long, J. R. Chem. Soc.
Rev. 2009, 38, 1294−1314. (c) Makal, T. A.; Li, J.-R.; Lu, W.; Zhou,
H.-C. Chem. Soc. Rev. 2012, 41, 7761−7779. (d) He, Y.-B.; Zhou, W.;
Qian, G.-D.; Chen, B.-L. Chem. Soc. Rev. 2014, 43, 5657−5678.
(2) (a) Kitagawa, S.; Uemura, K. Chem. Soc. Rev. 2005, 34, 109−119.
(b) Murdock, C. R.; Hughes, B. C.; Lu, Z.; Jenkins, D. M. Coord.
Chem. Rev. 2014, 258, 119−136. (c) Zhang, W.-X.; Liao, P.-Q.; Lin, R.-
B.; Wei, Y.-S.; Zeng, M.-H.; Chen, X.-M. Coord. Chem. Rev. 2014,
DOI: 10.1016/j.ccr.2014.12.009.
(3) Hu, S.; He, K.-H.; Zeng, M.-H.; Zou, H.-H.; Jiang, Y.-M. Inorg.
Chem. 2008, 47, 5218−5224.
(4) Zeng, M.-H.; Yin, Z.; Tan, Y.-X.; Zhang, W.-X.; He, Y.-P.;
Kurmoo, M. J. Am. Chem. Soc. 2014, 136, 4680−4688.
(5) (a) Horike, S.; Shimomura, S.; Kitagawa, S. Nat. Chem. 2009, 1,
695−704. (b) Schneemann, A.; Bon, V.; Schwedler, I.; Senkovska, I.;
Kaskel, S.; Fischer, R. A. Chem. Soc. Rev. 2014, 43, 6062−6096.
(6) (a) Zhang, J.-P.; Liao, P.-Q.; Zhou, H.-L.; Lin, R.-B.; Chen, X.-M.
Chem. Soc. Rev. 2014, 43, 5789−5814. (b) Kolea, G. K.; Vittal, J. J.
Chem. Soc. Rev. 2013, 42, 1755−1775. (c) Kawano, M.; Fujita, M.
Coord. Chem. Rev. 2007, 251, 2592−2605.
(7) (a) Yin, Z.; Zeng, M.-H. Sci. China: Chem. 2011, 54, 1371−1394.
(b) Zeng, M.-H.; Tan, Y.-X.; He, Y.-P.; Yin, Z.; Chen, Q.; Kurmoo, M.
Inorg. Chem. 2013, 52, 2353−2360.
F DOI: 10.1021/ic502650z
Article
(8) Horike, S.; Kishida, K.; Watanabe, Y.; Inubushi, Y.; Umeyama, D.;
Sugimoto, M.; Fukushima, T.; Inukai, M.; Kitagawa, S. J. Am. Chem.
Soc. 2012, 134, 9852−9855.
(9) Leong, W. L.; Vittal, J. J. Chem. Rev. 2011, 111, 688−764.
(10) (a) Murdock, C. R.; McNutt, N. W.; Keffer, D. J.; Jenkins, D. M.
J. Am. Chem. Soc. 2014, 136, 671−678. (b) Iremonger, S. S.; Liang, J.
M.; Vaidhyanathan, R.; Shimizu, G. K. H. Chem. Commun. 2011,
4430−4432.
(11) Shimomura, S.; Horike, S.; Matsuda, R.; Kitagawa, S. J. Am.
Chem. Soc. 2007, 129, 10990−10991.
(12) Seo, J.; Bonneau, C.; Matsuda, R.; Takata, M.; Kitagawa, S. J.
Am. Chem. Soc. 2011, 133, 9005−9013.
(13) (a) Leong, W. L.; Tam, A. Y. Y.; Batabyal, S. K.; Koh, L. W.;
Kasapis, S.; Yam, V. W. W.; Vittal, J. J. Chem. Commun. 2008, 3628−
3630. (b) Nakagawa, K.; Tanaka, D.; Horike, S.; Shimomura, S.;
Higuchia, M.; Kitagawa, S. Chem. Commun. 2010, 4258−4260.
(14) Ye, B.-H.; Tong, M.-L.; Chen, X.-M. Coord. Chem. Rev. 2005,
249, 545−565.
(15) (a) Sun, F.; Yin, Z.; Wang, Q.-Q.; Sun, D.; Zeng, M.-H.;
Kurmoo, M. Angew. Chem., Int. Ed. 2013, 52, 4538−4543. (b) Wu, G.-
Y.; Ren, Y.-X.; Yin, Z.; Sun, F.; Zeng, M.-H.; Kurmoo, M. RSC Adv.
2014, 4, 24183−24188.
(16) Deng, Q.-J.; Zeng, M.-H.; Liang, H.; Ng, S. W.; Huang, K.-L.
Acta Crystallogr., Sect. E 2006, m1293−m1295.
(17) (a) Zeng, M.-H.; Wang, Q.-X.; Tan, Y.-X.; Hu, S.; Zhao, H.-X.;
Long, L.-S.; Kurmoo, M. J. Am. Chem. Soc. 2010, 132, 2561−2563.
(b) Yin, Z.; Wang, Q.-X.; Zeng, M.-H. J. Am. Chem. Soc. 2012, 134,
4857−4863.
(18) (a) Kitagawa, H.; Ohtsu, H.; Kawano, M. Angew. Chem., Int. Ed.
2013, 52, 12395−12399. (b) Sava, D. F.; Rodriguez, M. A.; Chapman,
K. W.; Chupas, P. J.; Greathouse, J. A.; Crozier, P. S.; Nenoff, T. M. J.
Am. Chem. Soc. 2011, 133, 12398−12401. (c) Hasell, T.;
Schmidtmann, M.; Cooper, A. I. J. Am. Chem. Soc. 2011, 133,
14920−14923.
(19) Sheldrick, G. M. SADABS 2.05; University of Göttingen:
Göttingen, Germany, 2002.
(20) SHELXTL 6.10; Bruker Analytical Instrumentation: Madison,
WI, 2000.
(21) (a) Desiraju, G. R. Acc. Chem. Res. 2002, 35, 565−573.
(b) Steiner, T. Angew. Chem., Int. Ed. 2002, 41, 48−76.
(22) Wheeler, S. E. Acc. Chem. Res. 2013, 46, 1029−1038.
(23) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13.
(24) Nakamoto, K. Infrared and Raman Spectra of Inorganic and
Coordination Compounds; John Wiley and Sons: New York, 2009; pp
1−222.
(25) Dobrzańska, L.; Lloyd, G. O.; Raubenheimer, H. G.; Barbour, L.
J. J. Am. Chem. Soc. 2006, 128, 698−699.
(26) Murthi, M.; Snurr, R. Q. Langmuir 2004, 20, 2489−2497.
(27) DeBoer, G.; Burnett, J. W.; Young, M. A. Chem. Phys. Lett. 1996,
259, 568−573.
Inorg. Chem. XXXX, XXX, XXX−XXX