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■ INTRODUCTION
While major efforts are being devoted to metal−organic
between.9 In crystals, one can regard the ruggedness by the
presence of bulky groups protruding perpendicular to the chain
framework for the storage of fuel gases for the future safe compounds. A good example of this case is Zn(isophthalate)
and environmentally friendly use of hydrogen as our source of (derivatives of bipyridyine having different lengths) where the
energy,1 there is also some interest in the use of soft porous bpy bridges the Zn and one of the carboxylate bridges the zinc
crystals based on nonbonded chains or layers held by of an adjacent chain forming a ladder.11 Due to the protruding
supramolecular interactions.2,3 Interestingly, both systems benzenecarboxylate the efficient packing of the ladders is
carry their advantages and disadvantages. The former class hampered thus producing space between them. Such a strategy
has marginal variation of their void spaces through limited was successfully extended to different lengths of bpy to
allowable changes in bond distances and angles; thus, they are generate different sizes of cavities.12 Porosity has been observed
fairly rigid in most cases and in many cases retain their for structures with different packing motifs, including crisscross
crystallinity upon modifications.4 However, the latter has much and interdigitating of chains.3,13 Most important in the stability
more freedom of movement and can show a wider variety of of these structures is the supramolecular interactions, viz.,
structural properties,2,5 viz., reversible single-crystal-to-single- hydrogen bonds and π−π overlaps.
crystal (SC−SC), reversible single crystal to amorphous, and As the most versatile part of the entities forming the chains is
also nonreversible transformations.6,7 The flexibility and the organic ligands used, much of the known works concentrate
dynamics of the porous crystals have been studied on some on the use of linear spacer ligands coordinated to the metal ions
occasions. Such work became more prominent when Kitagawa in a linear fashion.9,14 In our previous study, 1H-benzimidazole-
and colleagues prepared several of these systems and studied 5-carbonate and its 2-site modified derivatives were widely used
their structural properties as well as their dynamics during gas to construct several 2D or 3D coordination polymers.15 In such
sorption.2a,5a They highlighted the great advantage of being able kinds of ligands, the imidazole can bind to one or two metal
to store more guests than in bonded frameworks.8 Examples ions based on the departure of 1-site hydrogen while the
based on both chains and layers have been reported,9,10 though carboxylate has numerous possibilities and the 2-site substituent
from a design point of view the former is more easily group can affect the final structure. Apparently, when the 1-site
controlled. Thus, there are few more linear chains ones. hydrogen is maintained, the ligand can be viewed as curving
Like matches in a box, the structure and shape of the match bridging spacer to construct 1D ribbon or zigzag chains.16
define the efficiency of the packing. When they are regular the
packing allows for no void space but when they are rugged or Received: November 3, 2014
irregular the packing is not so efficient, and voids are created in
Especially, the packing of such irregular chains may result in 5°/min. Calculated PXRD patterns were generated using Mercury
supramolecular structure with void space.3 On the basis of such 3.0.10 Raman spectra were obtained using a Renishaw inVia Raman
design, here we will present two solvated compounds, microscope equipped with a 785 nm diode laser and a 1200 lines/mm
{[Zn(ebic)2]·EtOH}n (1·EtOH) and {[Co(ebic)2]·H2O}n (2· grating. The high-pressure gas sorption measurements were performed
using the Belsorp HP-60 high-pressure sorption system. The C, H, and
H2O) where Hebic = 2-ethyl-1H-benzo[d]imidazole-5-carbox-
N microanalyses were carried out with a Vario Micro Cube elemental
ylic acid (Figure 1), which were obtained by solvothermal 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
Figure 1. (a) Molecular structure of Hebic. (b) The coordination (s), 1478 (m), 1456 (m), 1384 (s), 1078 (w), 1034 (w), 818 (m), 782
environment of M(II) center. (c) Perspective view of the 1D (m).
[M(ebic)2]n chain. 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.
technique. Importantly, the 1D chain formed has a kink
Synthesis of {[Co(ebic)2]·H2O}n (2·H2O). A mixture of Co-
imposed by the tetrahedral metal center that impaired the (NO3)2·6H2O (291 mg, 1.0 mmol), Hebic (60 mg, 0.31 mmol), NaN3
packing efficiency where the void space is taken up by the (20 mg, 0.31 mmol), and H2O (8 mL) was sealed in a Teflon-lined
ethanol and water. They display reversible SC−SC and single- steel autoclave and heated at 170 °C for 3 days. After the autoclave has
crystal to amorphous transformations, gas sorption, and most been cooled at a rate of 10 °C h−1 to 25 °C, the blue prismatic shaped
importantly iodine inclusion and releasing properties, including crystals of 2·H2O were collected, washed with H2O, and dried in air
electrical conductivity. (yield: 45.2 mg, 32% based on ligand Hebic). The phase purity of the
This work complements the recent research by us4,17 and bulk product was confirmed by PXRD and elemental analyses (%)
others18 on the inclusion of iodine molecules in the channels of calculated for 2·H2O (C20H20N4O5Co): C, 51.73; H, 4.56; N, 12.06.
porous crystalline materials in view of introducing polarizability 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
and conductivity as well as the storage of radioactive iodine that
(s), 702 (m).
is a major waste of the nuclear industries and its use in Synthesis of {[Co(ebic)2] }n (2). Compound 2 was obtained by
medicine.
■
heating crystals of 2·H2O under dynamic vacuum at 150 °C for 12 h.
The crystals retain their purple color.
EXPERIMENTAL SECTION Synthesis of {[Zn(ebic)2]·xI2 }n (1⊃xI2) and {[Co(ebic)2]·x′I2}n
Materials and Physical Measurements. Thermogravimetric (2⊃x′I2). Crystals of 1 and 2 (100 mg) were, respectively, soaked in 20
analyses (TGA) were performed on a SETARAM LABSYS evo mL of 0.1 mol L−1 cyclohexane solution of iodine for 8 days at
TGA instrument in flowing N2 at a heating rate of 5 °C per minute in different temperatures. The values of x and x′ were confirmed by TG
the range 25−800 °C. Powder X-ray diffraction (PXRD) intensities and EA: x = 0.55, 0.65, 1.00, and 1.30 and x′ = 0.60, 0.70, 1.00, 1.30 for
were measured at 293 K on a Rigaku D/max-IIIA diffractometer (Cu the temperature of 30, 50, 80, and 100 °C, respectively. TG curves are
Kα, λ = 1.540 56 Å). The crystalline powder samples were prepared by shown in Supporting Information Figure S6, and the calculated and
crushing the crystals and the PXRD scanned from 5 to 60° at a rate of observed values are listed in Supporting Information Table S3. The
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 Article
data of calculated and observed elemental analyses are given in steric hindrance between {M2(ebic)2} and improve the stability
Supporting Information Table S4. of the 1D [M(ebic)2]n chains.
X-ray Crystallography. Single-crystal X-ray diffraction (XRD) The 1D chains are connected to each other into a 3D
data collection for 1·EtOH was conducted on a Bruker SMART APEX supramolecular network (Figure 2a) via strong N−H···O
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 Figure 2. (a) Hydrogen bonding and π···π interactions between
found in the Supporting Information or can be obtained free of charge adjacent chains for 1·EtOH. (b) 3D supramolecular network showing
from the Cambridge Crystallographic Data Centre via http://www. the 1D channels in 1·EtOH.
ccdc.cam.ac.uk/data_request/cif.
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 cyclohexane solution of I2.26 It should be noted that the iodine
the vibration of I2 in interaction with the networks. In order to content is high to about 23.6−36.7% (wt %).
make clear how many I2 molecules fill the channels, PXRD, TG, When the crystalline solids of 1⊃xI2 were soaked in
and EA of the samples of 1 and 2, soaked in the cyclohexane methanol for 10 min, the color of the solids changed from
solution of I2 at different temperatures (30, 50, 80, and 100 black, to brown, then yellow to colorless, being an opposite
°C), have been measured. Most of the peaks in the PXRD of progress to captured I2, and the color of the methanol solution
1⊃xI2 remained at similar 2θ positions but were distinctly deepened gradually from colorless to dark yellow, which
weakened and broadened (Supporting Information Figure S5).
explained that the sorption and desorption of I2 are reversible.
The change of intensity and width indicates that the resulting
Meanwhile, the desorption of I2 in 2 has also been observed by
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 the following experiments: 10 mg 1⊃0.65 I2 and a piece of KI
PXRD are distinctly weakened, but when the I2 was removed test paper were placed into a sealed vial together, and then KI
from the framework upon immersing the crystals in methanol test paper gradually turned blue (Supporting Information
the peaks appeared again (Supporting Information Figure S5). Figure S8).
The unusual phenomenon can be explained by the high amount To further investigate the kinetics of I2 delivery of 1⊃xI2 and
of iodine in 1⊃xI2 that has a significant impact on the 2⊃x′I2 in crystal transformation, UV−vis spectra were recorded
crystallinity. Thus, PXRD of 1⊃xI2 and 2⊃x′I2 exhibited similar at room temperature as a function of time (Figure 8). The
patterns to those of 1 and 2, respectively.17 absorbance of I2 in methanol increases linearly with time before
TG curves (Supporting Information Figure S6) and EA 26 min for 1⊃xI2 and 2⊃x′I2, then it became slowly increasing
measurements indicate that x = 0.55, 0.65, 1.00, and 1.30 and x′ linearly with the time.17
= 0.60, 0.70, 1.00, 1.30 when the temperature is 30, 50, 80, and Electrical Conductivity. Iodine is known to be an
100 °C, respectively. It is noticeable that the captured amounts interesting instant visual probe to study host−guest inter-
of I2 increase with temperature, which suggests that the actions, and it can also introduce electrical conductivity. The
channels are flexible and enlarge with temperature (Supporting electrical conductivities of 1⊃0.55 I2 and 2⊃0.60 I2 are 3.47×
Information Figure S7). Most importantly, when the temper-
10−7 and 2.21 × 10−7 S/cm, respectively. They are nearly 80
ature is 100 °C, 1 and 2 can trap more I2 than that of the
maximally filled closely packed solid I2 in the corresponding and 90 times that for 1 and 2. Meanwhile, the values are lower
channels at room temperature (0.57 g/g). In comparison, the than that for solid I2 (7.69 × 10−6 S/cm) and much less than
uptake of I2 (0.31 and 0.35, 0.37 and 0.41, 0.56, and 0.57 g/g for those MOFs with I2 loading (σ∥ = 3.42 × 10−3 and σ⊥= 1.65
for 1 and 2, respectively) at 30, 50, and 80 °C is remarkable and × 10−4 S/cm),17 which may be attributed to the four close
comparable with zeolite 13X (0.32−0.38 g/g, with 10 Å pore), parallel iodine chains are restricted within well-regulated
and those (0.74 and 0.75 g/g for 1 and 2, respectively) at 100 aromatic channels, inducing high efficiency of n → π*
°C are comparable with activated carbon (0.84 g/g) in the charge-transfer (CT).27
E DOI: 10.1021/ic502650z
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article
■ CONCLUSION
Two porous supramolecular networks with 1D channels were
(8) Horike, S.; Kishida, K.; Watanabe, Y.; Inubushi, Y.; Umeyama, D.;
Sugimoto, M.; Fukushima, T.; Inukai, M.; Kitagawa, S. J. Am. Chem.
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obtained from 1D rigid coordination polymers with hydrogen (9) Leong, W. L.; Vittal, J. J. Chem. Rev. 2011, 111, 688−764.
bonding acceptors and donors, and conjugated aryl rings, which (10) (a) Murdock, C. R.; McNutt, N. W.; Keffer, D. J.; Jenkins, D. M.
are linked to each other by strong hydrogen bonds and π···π J. Am. Chem. Soc. 2014, 136, 671−678. (b) Iremonger, S. S.; Liang, J.
stacking. The 1D channels of the 3D networks are filled with M.; Vaidhyanathan, R.; Shimizu, G. K. H. Chem. Commun. 2011,
solvent molecules. SC−SC transformation confirms the 4430−4432.
channels are retained after the removal of the solvents. The (11) Shimomura, S.; Horike, S.; Matsuda, R.; Kitagawa, S. J. Am.
desolvated compounds exhibited fast and reversible iodine Chem. Soc. 2007, 129, 10990−10991.
uptake with visible color change, and the uptake increased with (12) Seo, J.; Bonneau, C.; Matsuda, R.; Takata, M.; Kitagawa, S. J.
Am. Chem. Soc. 2011, 133, 9005−9013.
temperature due to the channel expansion upon heating, which (13) (a) Leong, W. L.; Tam, A. Y. Y.; Batabyal, S. K.; Koh, L. W.;
demonstrates that these compounds are dynamic and exhibit Kasapis, S.; Yam, V. W. W.; Vittal, J. J. Chem. Commun. 2008, 3628−
elastic guest accommodations. Iodine loaded crystals showed 3630. (b) Nakagawa, K.; Tanaka, D.; Horike, S.; Shimomura, S.;
80 times higher electrical conductivity compared to the guest Higuchia, M.; Kitagawa, S. Chem. Commun. 2010, 4258−4260.
free ones; even the capsuled iodine was arranged with disorder (14) Ye, B.-H.; Tong, M.-L.; Chen, X.-M. Coord. Chem. Rev. 2005,
in the irregular channels. 249, 545−565.
■
(15) (a) Sun, F.; Yin, Z.; Wang, Q.-Q.; Sun, D.; Zeng, M.-H.;
ASSOCIATED CONTENT 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.
*
S Supporting Information 2014, 4, 24183−24188.
Crystallographic data in CIF format, and additional plots and (16) Deng, Q.-J.; Zeng, M.-H.; Liang, H.; Ng, S. W.; Huang, K.-L.
data for the complexes in PDF format. This material is available Acta Crystallogr., Sect. E 2006, m1293−m1295.
free of charge via the Internet at http://pubs.acs.org. (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.
AUTHOR INFORMATION (b) Yin, Z.; Wang, Q.-X.; Zeng, M.-H. J. Am. Chem. Soc. 2012, 134,
4857−4863.
Corresponding Author (18) (a) Kitagawa, H.; Ohtsu, H.; Kawano, M. Angew. Chem., Int. Ed.
*E-mail: zmh@mailbox.gxnu.edu.cn. 2013, 52, 12395−12399. (b) Sava, D. F.; Rodriguez, M. A.; Chapman,
Notes 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.;
The authors declare no competing financial interest.
■
Schmidtmann, M.; Cooper, A. I. J. Am. Chem. Soc. 2011, 133,
14920−14923.
ACKNOWLEDGMENTS (19) Sheldrick, G. M. SADABS 2.05; University of Göttingen:
This work was supported by NSFC (nos. 21371037, Göttingen, Germany, 2002.
(20) SHELXTL 6.10; Bruker Analytical Instrumentation: Madison,
91422302), Funds for Doctoral Discipline of University
WI, 2000.
(20134504110001), Guangxi Province Science Funds (21) (a) Desiraju, G. R. Acc. Chem. Res. 2002, 35, 565−573.
(2012GXNSFFA060001, 2014GXNSFFA118003), Bagui (b) Steiner, T. Angew. Chem., Int. Ed. 2002, 41, 48−76.
Scholar Program (2014A001), and Talents Highland of (22) Wheeler, S. E. Acc. Chem. Res. 2013, 46, 1029−1038.
Molecular Solid Materials of Guangxi Province in China. (23) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13.
M.K. is supported by CNRS-France. (24) Nakamoto, K. Infrared and Raman Spectra of Inorganic and
■
Coordination Compounds; John Wiley and Sons: New York, 2009; pp
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F DOI: 10.1021/ic502650z
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