Article pubs.acs.org/crystal
Single- and Double-Layer Structures and Sorption Properties of Two Microporous Metal−Organic Frameworks with Flexible Tritopic Ligand Liqin Han,† Yan Yan,‡ Fuxing Sun,*,‡ Kun Cai,† Tsolmon Borjigin,‡ Xiaojun Zhao,‡ Fengyu Qu,*,† and Guangshan Zhu‡ †
Department of Photoelectric Band Gap Materials, Key Laboratory of Ministry of Education, College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China ‡ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, P. R. China. S Supporting Information *
ABSTRACT: Two 2D multifunctional microporous metal− organic frameworks, [Cd3(L)2(H2O)6]·1.5H2O·2EtOH·DMF (1, H3L = 2,4,6-tris-(4-carboxyphenoxy)-1,3,5-triazine) and [Zn3(L)2(H2O)2]·3H2O·TEA·2DMF (2), with single- and double-(6,3)-layer structures, respectively, have been synthesized by the reaction of Cd(Zn) nitrate with H3L in a mixed solvent of DMF, ethanol, and H2O. TGA and PXRD analysis showed that compounds 1 and 2 were thermally stable up to 250 °C. Gas sorption measurement indicates that compounds 1 and 2 exhibited selective sorption capabilities for CO2 over CH4 and N2 and could adsorb considerable amounts of H2 at low temperature. These two compounds also showed high sorption capabilities for water, methanol, and ethanol vapors. The highest adsorption amounts of compounds 1 and 2 are 168.8 and 257.3 cc/g for H2O, 175.1 and 140.8 cc/g for methanol, and 91.7 and 76.2 cc/g for ethanol, respectively. Furthermore, the maximum luminescence emission peaks of compounds 1 and 2 exhibit blue shifts of 138 and 132 nm, respectively, compared to the free ligand.
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INTRODUCTION In the past decade, metal−organic frameworks (MOFs), also called porous coordination polymers, have received intense attention because of their enormous variety of interesting structures and great potential applications as functional materials.1−8 These materials can be applied potentially in gas storage, separation, ion exchange, catalysis, sensor, drug delivery, and so on.9−20 The structures of many porous MOFs are produced by taking advantage of the well-defined coordination geometries of metal centers as nodes and polyatomic organic bridging ligands as linkers.21,22 To obtain predictable frameworks and properties, a large number of studies are being focused on constructing novel coordination polymers by using functional metal ions and versatile organic ligands.23−25 Among numerous ligands to form various MOF structures, tritopic ligands are widely used because of topological features of tritopic ligands. Three-node nets such as 1,3,5-benzenetricarboxylate (BTC), 4,4′,4″-benzene-1,3,5triyl-tribenzoate (BTB), 4,4′,4″-s-triazine-2,4,6-triyltribenzoate (TATB), and 1,3,5-benzenetristetrazolate (BTT) have been used to form many famous MOFs.26−31 On the other hand, the use of a flexible ligand to construct porous coordination polymers has increased because of the advantages associated with their uses, such as adaptive recognition properties and breathing ability in the solid state.32,33 The use of flexible © 2013 American Chemical Society
ligands may generate novel complexes with not only attractive sorption properties but also interesting topologies, as flexible ligands have numerous conformations and coordination modes observed in the coordination process.34−37 Moreover, a variety of conformations of the flexible ligands imposed by the coordination geometry of the metal ion and the final 3D packing would lead to the richness and unpredictability of the formed MOF structures. Hence, it is still a significant challenge to assemble desired MOFs with great sorption properties and interesting structures using flexible organic ligands. Recently, all kinds of triazine derivatives have been extensively used to construct MOFs that exhibit excellent thermal stable structures and permanent porosity.5,38,39 The triazine derivatives could give vastly different structures because the electron-deficient triazine ring would have strong offset face-to-face interactions.40,41 The increased quadrupole moment of the triazine ring makes them more suitable for π−π stacking,42 which would strengthen the thermal stability of the resulting MOFs. Compared to benzene derivatives, triazine derivatives were more likely to give complexes with high thermal stability because they were used as a monomer for the Received: October 23, 2012 Revised: March 8, 2013 Published: March 11, 2013 1458
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preparation of high-temperature-resistant polymers.43 In addition, for benzene derivatives such as BTB, repulsions between the C−H bonds on the central ring and those on the peripheral rings play a key role in controlling the conformation of the ligand; the triazine derivative ligands with no C−H bonds on the central ring are not subject to such repulsions, which makes them flatter than benzene derivatives. Considering the thoughts above, we designed and synthesized a flexible tritopic ligand, 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3L, Scheme 1). On the basis of this ligand, two microporous
Synthesis of Compound 2. The procedure was the same as that for compound 1 except that Cd(NO3)2·4H2O was replaced by Zn(NO3)2·6H2O (24 mg, 0.1 mmol). Yield: 76% (based on H3L). EA (%) calcd for C60H59N9O25Zn3 (Mr 1500): C, 48.00; H, 3.93; N, 8.40. Found: C, 47.86; H, 4.31; N, 8.59. The IR spectrum of compound 2 is shown in Figure S1. X-ray Structure Determination and Structure Refinement. Xray intensity data of 1 and 2 were collected on a Bruker SMART APEX CCD diffractometer using graphite monochromatized Mo Kα radiation (λ = 0.710 73 Å).45 An empirical absorption correction was applied to the data using the SADABS program. The structures were solved by direct methods (SHELXS). All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on benzene rings were fixed at calculated positions and refined by using a riding mode. The data of compound 1 twinned were divided into four sets of overlapped reflections. During refinement the structure was solved with the subdata set taken from the major domain and then refined against the component data set using the HKLF 5 format. All reflections are treated as independent, and no value of R(int) is provided. The ratio of the twin components could be refined using the BASF command (which refined to ∼25%, ∼25%, ∼25%). The large volume fractions of solvents in the lattice pores of compound 2 were treated using the SQUEEZE routine in the PLATON software package.46,47 All calculations were performed using the SHELXTL program.48 The crystallographic data are summarized in Table S1 and the selected bond lengths and bond angles of these two compounds are listed in Table S2 in the Supporting Information.
Scheme 1. Structure of Ligand H3L
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MOFs, [Cd3 (L) 2 (H 2O) 6 ]·1.5H 2 O·2EtOH·DMF (1) and [Zn3(L)2(H2O)2]·3H2O·TEA·2DMF (2), which have singleand double-(6,3)-layer structure, respectively, have been synthesized. The sorption measurements demonstrate that they are microporous materials with selective sorption for CO2 over CH4 and N2. In addition, they can adsorb a considerable amount of H2 at low temperature and high amounts of water, methanol, and ethanol vapors at room temperature. Compounds 1 and 2 have emission maxima at 416 nm (λex = 306 nm) and 422 nm (λex = 308 nm), respectively, whereas the H3L ligand displays the emission maxima at 554 nm (λex = 307 nm).
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RESULTS AND DISCUSSION
Crystal Structures. Single crystal X-ray diffraction studies reveal that compound 1 crystallizes in the trigonal space group P3̅ exhibiting a two-dimensional framework with single-(6,3)layers. In the asymmetric unit of compound 1, there are three Cd(II) ions lying on the 3-fold axis, two-thirds of L3− ligands with facial C3 symmetry and two-thirds with terminal H2O. As shown in Figure 1a, Cd1 is six-coordinated in an octahedral coordination environment, defined by six oxygen atoms of three chelating bidentate carboxylate groups from different ligands. Cd2 and Cd3 are held together by three carboxylate groups to yield a binuclear [Cd2(COO)3] unit in which they
EXPERIMENTAL SECTION
Materials and Methods. The ligand 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3L) was prepared according to the literature.44 All other chemical reagents were purchased from commercial sources and were used without further purification. Fluorescence spectroscopy data were recorded on a LS55 luminescence spectrometer. Elemental analyses (C, H, and N) were carried out on a Perkin-Elmer 240 analyzer. FT-IR spectra were recorded as KBr pellets with a Nicolet Impact 410 FT-IR spectrometer, using the reflectance technique (4000−400 cm−1). Thermogravimetric analysis (TGA) curves were collected on a Perkin-Elmer TGA 7 thermogravimetric analyzer with a heating rate of 10 °C/min in air atmosphere. Powder X-ray diffractions (PXRD) were carried out on Scintag X1 diffractometer with Cu Kα (λ = 1.5418 Å) at 40 kV, 35 mA. Low pressure gas and vapor adsorption measurements were performed with Autosorb-iQ2-MP-AG machine. CO2 (195 K) sorption measurements was performed using a Micromeritics ASAP 2010 instrument. Synthesis of Compound 1. A mixture of H3L (24 mg, 0.049 mmol) and Cd(NO3)2·4H2O (23 mg, 0.075 mmol) was dissolved in a mixed solvent of DMF (2.5 mL), EtOH (2.5 mL), H2O (1 mL), and triethylamine (TEA, 0.02 mL) at room temperature. HNO3 (2 M) was added dropwise until the mixture became clear. The mixture was standing at 60 °C for 3 days to give colorless block-shaped crystals. Yield: 78% (based on H3L). EA (%) calcd for C55H46N7O29.5Cd3 (Mr 1596): C, 40.94; H, 2.85; N, 6.08. Found: C, 41.08; H, 3.17; N, 5.84. The IR spectrum of compound 1 is shown in Figure S1 in Supporting Information.
Figure 1. (a) Coordination environment for Cd atoms in compound 1 (symmetry code, a, −y + 1, x − y + 1, z; b, −x + y, −x + 1, z). (b) Schematic description of the (6,3)-layer. (c) Packed layers of compound 1: A, green; B, purple; C, red; D, blue. (d) Compound 1 demonstrating the open micropores along the c axis. 1459
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further pack a 3D supramolecular open framework in an AB fashion via π−π stacking interactions (3.759 Å) of triazine rings between the adjacent layers (Figure 2c). The framework also has 1D channels with a size of about 4.5 × 4.5 Å2 (measured distance between opposite atoms) along the c axis (Figure 2d). After the removal of guest solvent and coordinated water molecules, compound 2 shows 41.4% void volume according to PLATON calculations.49 Thermal Stabilities. The thermal stabilities of compounds 1 and 2 have been studied using thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). The TGA curve of compound 1 (Figure S2) shows that the first weight loss of 6.28% was from 35 to 200 °C, which corresponds to the loss of guest ethanol and H2O molecules (calculated, 6.89%). The second weight loss of 11.24% was from 200 to 300 °C corresponding to the loss of guest DMF molecules and terminal H2O molecules (calculated, 10.59%). Decomposition of compound 1 began at about 300 °C. The residue was CdO (experimental, 23.93%; calculated, 24.06%). Similar to compound 1, the TGA curve of compound 2 (Figure S3) shows a weight loss of 10.67% between 35 and 160 °C, corresponding to the loss of three guest H2O and one guest TEA molecules (calculated, 10.34%). The second weight loss of 11.71% was from 160 to 350 °C, which can correspond to the loss of the guest DMF and terminal H2O molecules (calculated, 11.87%). Decomposition of compound 2 began near 360 °C. The residue was ZnO (experimental, 15.90%; calculated, 16.20%). PXRD studies were performed for the as-synthesized sample, and the samples were heated at different temperatures including 215, 250, and 300 °C. (Figures S4 and S5). The PXRD patterns of these two compounds heated at 215 and 250 °C for 2 h were coincident with the patterns of their assynthesized samples, which indicates that the departure of the guest molecules does not lead to an obvious phase transformation. When the sample was heated to 300 °C, coordinated solvent molecules began to depart, which causes a structural transformation with a decrease in crystallinity. Sorption Properties. The permanent porosity of compounds 1 and 2 is confirmed by their sorption capacities. Before the measurement, the as-synthesized samples were soaked in methanol for 3 days and then evacuated at 215 °C for 12 h to obtain their activated samples. The N2 sorption properties of these two compounds at 77 K were measured. However, they only show very small N2 sorption volume, 17.5 and 13.3 cc/g for compounds 1 and 2, respectively (Figures S6 and S7). CO2 (195 K) sorption measurements for desolvated 1 and 2 gave type I isotherms for microporous materials (Figures S10 and S11), given calculated Langmuir surface areas of 417 and 535 m2/g for 1 and 2, respectively. The adsorption−desorption isotherms of compound 1 for CO2 at 273 and 298 K are plotted in Figure 3a. As shown, compound 1 exhibits a typical type I reversible sorption for CO2. At 273 K and 1 atm, compound 1 could take up 11.0 wt % of CO2 (62.94 cc/g), and at 298 K the CO2 uptake by compound 1 is 8.4 wt % (46.8 cc/g). Correspondingly, compound 1 could only adsorb 24.5 cc/g CH4 at 273 K and 1 atm, which is also shown in Figure 3a. Compound 2 has similar selective adsorption abilities for CO2 over CH4. As shown in Figure 3b, compound 2 could adsorb 8.1 wt % (44.86 cc/g) and 5.7 wt % of CO2 (31.0 cc/g) at 273 and 298 K, respectively. However, the CH4 uptake of compound 2 is only 1.1 wt % (14.01 cc/g) at 273 K and 1.0 atm. To assess the values of the CO2 adsorption enthalpies in these compounds, the 273 and 298 K data were then fit
show similar octahedral coordination geometries completed by three oxygen atoms from individual H3L ligands and three oxygen atoms from terminal H2O. The bond lengths of Cd1− O, Cd2−O, and Cd3−O are in the ranges of 2.246(4)− 2.316(4), 2.156(9)−2.274(4), and 2.100(10)−2.201(3) Å, respectively. Each Cd1 is linked by three L3−, and each L3− links three Cd1 ions to form a (6,3)-layer along the ab plane. On the other side, the binuclear [Cd2(COO)3] units combine L3‑ ligands in a similar way to construct another kind of (6,3)layer along ab plane. These single-layers further stack into ABCD packing fashion by the face-to-face π−π interactions between the triazine rings of adjacent layers to form a threedimensional supramolecular open framework. As shown in Figure 1c, layers A and D are constructed by Cd1 and the ligands, and layers B and C are formed by [Cd2(COO)3] units and the ligands. Interestingly, layer A rotating 60° clockwise would overlap the layer D, and similarly, a 60° clockwise rotation of layer B would overlap layer C. The layer packing framework has 1D open rhombic channels of approximately 5 × 8 Å2 (measured distance between opposite atoms) along the c axis (Figure 1d). After elimination of guest water and coordinated water molecules, the total accessible volume in compound 1 is 41.5% using the PLATON/VOID routine.49 Single crystal X-ray crystallography reveals that compound 2 crystallizes in the trigonal space group P31̅ c with a 2D double(6,3)-layers framework. The asymmetric unit of compound 2 contains one-third Zn2 ions, one-sixth Zn1 ions, one-third L3− ligands, and one-third terminal H2O. As shown in Figure 2a,
Figure 2. (a) Coordination environment of Zn(II) atoms in compound 2 (symmetry code, a, 1 − y, 1 − x, 0.5 − z; b, 1 − y, 1 + x − y, z; c, x, 1 + x − y, 0.5 − z; d, −x + y, 1 − x, z; e, −x + y, y, 0.5 − z). (b) One double-(6,3)-layer in compound 2. (c) Packed doublelayers of compound 2. (d) Compound 2 demonstrating the open micropores along the c axis.
Zn1 is coordinated by six oxygen atoms from six distinct L3− ligands in an octahedral geometry. Zn2 and Zn2a are similarly four-coordinated in a tetrahedron environment supplied by three carboxylate oxygen atoms from different L3− ligands and one oxygen atom from terminal H2O. The bond lengths of Zn1−O and Zn2−O are 2.079(4) and 1.923(5) Å, respectively. These groups form a trinuclear [Zn3(COO)6] unit. Each [Zn3(COO)6] units is linked by six L3− ligands to form a double-(6,3)-layer (Figure 2b). The infinite double-layers 1460
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Figure 4. H2 sorption isotherms of compound 1 (a) and compound 2 (b).
Figure 3. CO2 and CH4 sorption isotherms of compound 1 (a) and compound 2 (b).
simultaneously using a virial equation.31,50 The isosteric heat of adsorption curves give an initial heat of ∼31 kJ/mol (Figure S8). These values are comparable with other reported flexible structures having similar porosity at similar temperatures, for example, MIL-53(Cr) (32 kJ/mol) and MIL-53(Al) (35 kJ/ mol).51 The selective sorption capabilities of compounds 1 and 2 for CO2 over CH4 and N2 could be explained by a sizeexclusion behavior of the small channels and special layer structures tuned by the π−π stacking interactions in the structures of these two compounds. Compounds 1 and 2 also have the ability to adsorb considerable amounts of H2 at low temperatures. As shown in Figure 4, compounds 1 and 2 show substantial H2 sorption that increased linearly as H2 pressure increased, giving the highest uptakes of 1.17 and 1.02 wt % at 77 K and 1.0 atm, respectively. The initial enthalpy of compounds 1 and 2 were calculated to be 7.6 and 7.3 kJ/ mol, respectively (Figure S9). The porosity of compounds 1 and 2 also allow potential access by a variety of small solvent molecules. We examined the vapor sorption abilities including water, methanol, and ethanol of compounds 1 and 2 at room temperature. These measurements were also carried out on the actived samples. As shown in Figure 5a, compound 1 exhibits a hysteretic adsorption behavior to water and type I behavior with small hysteresis to methanol and ethanol. Water was gradually adsorbed onto compound 1 in the low-pressure region, and the uptake increased as the vapor pressure increased. Finally, it took up a certain amount of water, 168.8 cc/g at P/P0 = 1. The methanol and ethanol sorption isotherms were characterized by a plateau reached at low relative pressure, which is indicative of
Figure 5. Water, methanol, and ethanol sorption isotherms of compound 1 (a) and compound 2 (b) measured at 298 K. 1461
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[Zn3(L)2(H2O)2]·3H2O·TEA·2DMF (2) with single- and double-(6,3)-layer structures, respectively, have been successfully synthesized and characterized. Compounds 1 and 2 display high thermal stability and permanent porosity. The gas sorption measurements indicate that compounds 1 and 2 have selective sorption capabilities for CO2 over CH4 and N2 and adsorbed considerable amounts of H2 at low temperature. These two compounds also show high sorption capabilities for water, methanol, and ethanol vapors, which proves that they are good porous material with flexible frameworks. Furthermore, compounds 1 and 2 both show luminescence emissions with blue shifts compared to the ligand.
sorption in micropores. The highest methanol and ethanol vapor adsorptions on compound 1 are 175.1 and 91.7 cc/g, respectively. For compound 2, as shown in Figure 5b, the methanol and ethanol adsorption isotherms are similar to that of compound 1 and are of type I behavior with small hysteresis. At saturated vapor pressures, compound 2 can adsorb the highest amounts of the methanol and ethanol with values of 140.8 cc/g and 76.2 cc/g, respectively. The water adsorption of compound 2 was different, which gradually increases to a small uptake of 87.0 cc/g at P/P0 = 0.40, then suddenly jumps to 186.6 cc/g at P/P0 = 0.56, and gradually reaches a saturation uptake of 257.3 cc/g at P/P0 = 0.95 with notable hysteresis; thus, it can be classified as type V. A similar phenomenon was also reported for a number of flexible MOFs, which could result from the flexible frameworks and the interaction between the framework and the guest.52,53 Moreover, the water adsorption isotherm of compound 2 can be attributed to “gate-open behavior”, in which retaining a large amount of guest molecules at very low relative pressure can arise from strong host−guest interaction and/or a large diffusion barrier.54−58 Photoluminescent Properties. The photoluminescence of d10 metal complexes has been attracting intensive research interest, owing to their potential applications in chemical sensors, photochemistry, and electroluminescent (EL) displays.59−61 To study the photoluminescent properties of compounds 1 and 2, the emission spectra of 1 and 2 in the solid state were investigated at room temperature (Figure 6). It
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ASSOCIATED CONTENT
S Supporting Information *
One file containing crystallographic data, selected bond lengths and bond angles, IR, PXRD, TGA curves, N2 and CO2 adsorption isotherms, Qst of CO2 adsorption curves and Qst of H2 adsorption curves; two files of crystallographic information in CIF format; two files containing results from checkCIF/PLATON. This material is available free of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
*For F.S.: e-mail,
[email protected]. For F.Q.: e-mail,
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS Financial support for this study was provided by the National Native Science Foundation of China (Grants 21171045 and 21101046), Innovation Special Fund of Harbin Science and Technology Bureau of China (Grant 2010RFXXS055), Program for Scientific and Technological Innovation Team Construction in Universities of Heilongjiang Province (Grant 2011TD010), Doctoral Initiation Fund of Harbin Normal University (Grant 20102329110002), National Basic Research Program of China (Program 973, Grant 2012CB821700), Major International (Regional) Joint Research Project of NSFC (Grant 21120102034), and NSFC (Grant 20831002).
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Figure 6. Solid-state emission spectra of compounds 1 and 2 at room temperature.
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is shown that compounds 1 and 2 have emission maxima at 416 nm (λex = 306 nm) and 422 nm (λex = 308 nm), respectively, whereas the H3L ligand displays the emission maxima at 554 nm upon excitation at 307 nm. In comparison with the free ligand, blue shifts of 138 and 132 nm occur in the maximum emission peaks in compounds 1 and 2. The luminescence of 1 and 2 should be ascribed as the metal-to-ligand charge transfer (MLCT).62 The ligand chelation to the metal center may effectively increase the rigidity of the ligand and reduce the loss of energy by radiationless decay, thus causing the blue shift in 1 and 2. Two microporous metal−organic frameworks [Cd3(L)2(H2O)6]·1.5H2O·2EtOH·DMF (1, H3L = 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine) and 1462
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Crystal Growth & Design
Article
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dx.doi.org/10.1021/cg301559s | Cryst. Growth Des. 2013, 13, 1458−1463
