ARTICLE pubs.acs.org/crystal
Two Novel Zinc(II) MetalOrganic Frameworks Based on Triazole-Carboxylate Shared Paddle-Wheel Units: Synthesis, Structure, and Gas Adsorption Yun Ling,†,‡ Zhenxia Chen,†,‡ Hua Zheng,† Yaming Zhou,*,† Linhong Weng,† and Dongyuan Zhao†,‡ † ‡
Department of Chemistry, Fudan University, Shanghai 200433, China Laboratory of Advanced Materials, Fudan University, Shanghai 200433, China
bS Supporting Information ABSTRACT: Two novel porous metalorganic frameworks {Zn7(btc)4(dmtrz)2(H2O)5}n (1) and {[Zn6(btc)4(dmtrz)3] 3 3H3O 3 2H2O}n (2) (H3btc = 1,3,5-benzenetricarboxylic acid, Hdmtrz = 3,5-dimethyl-1H-1,2,4-triazole) have been solvothermally synthesized. Single-crystal structure analysis reveals that both structure 1 and 2 contain special triazole-carboxylate shared paddle-wheel units. The crucial factors to the assembly of such paddle-wheel units are discussed. Gas adsorption studies suggest that 2 is a potential microporous material for adsorptive separation of CO2 over N2.
’ INTRODUCTION Metalorganic frameworks (MOFs), as a new class of porous materials, have attracted considerable attention during the past decades because of their potential applications in gas storage and separation, molecular recognition, ion exchange, heterogeneous catalysis, drug delivery, and so on.110 Generally, this new family of porous materials is constructed by metal ions or clusters as nodes and organic ligands as linkers.1016 The well-defined nodes, such as a [Zn4O(O2C)6] cluster,1721 [M2(O2C)4] (M = Co, Ni, Cu, Zn, Mo) paddle-wheel unit,2226 and [M3(μ3-O)(O2C)6] (M = Al, Sc, Cr, Fe, Ni, In) trigonal cluster,2734 are considered to be important in the field of crystal engineering.11 However, the uninodal evennumber connected networks, for example the pcu net based on [Zn4O(O2C)6]38 or [M2(O2C)4]3941 secondary building units (SBUs), seems to prefer self-interpenetration according to the topological analysis.14,3538 Since the multiconnected nets, especially when they are all odd number connected nets, are less self-interpenetrated,14,38 a general strategy is to adopt multitopic ligands,38,42 which are viewed as multiconnected nodes to form the multiconnected nets. Another feasible strategy is to use mixed ligands with multiconnectivities.38,4346 With the later method, a large number of porous MOFs have been synthesized. Recently, a highly porous MOF based on mixed ligands of 3,30 ,5,50 -tetramethyl-4,40 -bipyrazolate and 1,4-benzenedicarboxylate was reported.47 The [Zn4O(O2C)2(NN)4] SBU (Scheme 1a) is similar to the famous Zn4O(O2C)6 cluster, but four carboxylate groups are substituted by pyrazole groups. This structure indicates that pyrazole and carboxylate groups have similar coordination geometries and can be used to construct novel SBUs. Triazole (trz) ligands which combine the coordination geometries of both pyrazole r 2011 American Chemical Society
and imidazole have therefore drawn our attention (Scheme 1b). Based on the structural analysis of [M2(trz)2 ] SBUs4855 (Scheme 1c), the bending configuration of [M2(trz)2] will offer suitable coordinated space for carboxylate groups to construct novel triazole-carboxylate shared paddle-wheel SBUs. However, porous MOFs based on triazole-carboxylate shared paddle-wheel units are rarely reported, as far as we know. Herein, we report the synthesis of two novel porous MOFs constructed by mixed triazole and carboxylate ligands, namely {Zn7(btc)4(dmtrz)2(H2O)5}n (1) and {[Zn6(btc)4(dmtrz)3] 3 3H3O 3 2H2O}n (2) (H3btc = 1,3,5-benzenetricarboxylic acid, Hdmtrz = 3,5-dimethyl-1H-1,2,4-triazole). Single-crystal structure analysis reveals that structure 1 contains a triazole-carboxylate shared paddle-wheel [Zn2(O2C)2(NN)] SBU and a paddle-wheel [Zn2(O2C)3] SBU and that structure 2 contains a triazolecarboxylate shared paddle-wheel unit of [Zn2(O2C)2(NN)] and [Zn2(O2C)(NN)2]. Single-component gas adsorption of CO2 and N2 suggests that 2 could be a potential microporous material for adsorptive separation of CO2 over N2 at room temperature.
’ EXPERIMENTAL SECTION Materials and General Measurements. All reagents were purchased from commercial sources and used as received, except for Hdmtrz ligand, which was synthesized by the previously reported method.56 IR spectra were performed on a Nicolet 470 FT-IR spectrometer in the range Received: November 25, 2010 Revised: May 3, 2011 Published: May 27, 2011 2811
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Crystal Growth & Design Scheme 1. (a) Zn4O cluster constructed by edge-sharing of two carboxylate and four μ1,2-connected pyrazole groups; (b) coordination geometry of triazole ligands (R represents organic groups); (c) planar and bent [M2(trz)2] SBU
4000400 cm1 with KBr pellets. Elemental analyses of C, H, and N were carried out on the Elementar Vario EL III. Powder X-ray diffraction (PXRD) patterns were measured using a Bruker D8 powder diffractometer with Cu KR radiation (λ = 1.5406 Å). Thermogravimetric analyses (TGA) were carried out on TGA/SDTA 851 in the temperature range 30800 °C under N2 flow with the heating rate 10 °C 3 min1. Samples 1 and 2 were activated at 323 and 373 K, respectively, on IGA adsorption apparatus under vacuum conditions for 12 h before CO2 and N2 sorption measurements. Synthesis of {Zn7(btc)4(dmtrz)2(H2O)5}n (1). Zn(NO3)2 3 6H2O (0.3 mmol, 0.089 g) was dissolved in 5 mL of N,N0 -dimethylacetamide (DMAC) and added to the mixture solution of H3btc (0.2 mmol, 0.033 g) and Hdmtrz (0.2 mmol, 0.020 g) in 5 mL of DMAC. The solution was stirred at room temperature for 10 min, and then the mixture was transferred to a Teflon-lined stainless steel autoclave (15 mL) and heated at 140 °C for 3 days, followed by cooling to room temperature. Colorless block crystal products were collected by filtration (yield: 38% for 1 based on H3btc). Elemental analysis calcd for 1 (C44H34N6O29Zn7, 1568.36): C, 33.69; H, 2.18; N, 5.36%. Found: C, 33.40; H, 2.23; N, 5.31%. IR (KBr pellets, cm1): 3407(br), 2939(w), 1623(s), 1571(m), 1438(m), 1369(s), 1263(w), 1191(w), 1106(w), 1022(w), 937(w), 766(m), 721(m). Synthesis of {[Zn6(btc)4(dmtrz)3] 3 3H3O 3 2H2O}n (2). The synthesis procedure of 2 was similar to that of 1, except for replacing Zn(NO3)2 3 6H2O by Zn(OAc)2 3 4H2O. Colorless block crystal products were collected by filtration (yields: 41% for 2, based on H3btc). Elemental analysis calcd for 2 (C48H43N9O29Zn6, 15926.79): C, 35.98; H, 2.71; N, 7.87%. Found: C, 36.09; H, 2.66; N, 7.91%. IR (KBr pellets, cm1): 3430(br), 2933(w), 1625(s), 1569(m), 1438(m), 1369(s), 1103(w), 1022(w), 935(w), 767(m), 721(m). X-ray Crystallographic Study. Data collection for 1 and 2 was carried out on a Bruker Apex CCD diffractometer with graphite monochromated Mo KR radiation (λ = 0.71073 Å) at 293 K. Data reduction was performed with SAINT, and empirical absorption corrections were applied by the SADABS program.57 Structures were solved by direct methods using the SHELXS program and refined with the SHELXL program.58,59 Heavy atoms and other non-hydrogen atoms were directly obtained from a difference Fourier map. Final refinements were performed by full-matrix least-squares methods with anisotropic thermal parameters for all non-hydrogen atoms on F2. C-bonded H atoms were placed geometrically and refined as riding modes. H atoms of coordinated and lattice water were hardly positioned from difference Fourier maps because of disorder. The number of lattice water molecules in 2 was calculated based on TGA. Crystallographic data are listed in Table 1, and selected bond length and angles are listed in Table S1.
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Table 1. Crystal Data and Structure Refinements 1
2
empirical formula
C44H34N6O29Zn7
C48H43N9O29Zn6
formula weight
1568.36
1592.79
T (K)
293(2)
293(2)
wavelength (Å)
0.71073
0.71073
crystal system
orthorhombic
monoclinic
space group
Pna21
P21
a (Å)
25.117(11)
19.379(8)
b (Å) c (Å)
26.607(12) 17.479(8)
14.639(6) 19.484(7)
R (deg)
90
90
β (deg)
90
116.046(6)
γ (deg)
90
90
volume (Å3)
11681(9)
4966(3)
Z
4
2
Dcalc (g 3 cm3)
0.886
1.041
μ (mm1) collected/unique (Rint)
1.459 69499/21006 (0.138)
1.481 17517/10727 (0.059) 1.03
GOF on F2
1.01
R1/wR2 [I > 2σ(I)]
0.0851/0.2728
0.0797/0.2613
max/min ΔF [e Å3]
1.32/0.96
1.74/0.83
’ RESULTS AND DISCUSSION Synthesis and Characterization. Many examples have proven that amides such as N,N-dimethylformamide (DMF) and N, N-diethylformamide (DEF) can provide an efficient environment for the assembly of many types of MOFs based on metalcarboxylate clusters. Similarly, 1 and 2 were solvothermally synthesized by the reaction of H3btc, Hdmtrz, and Zn(II) salt with a molar ratio of 1:1:1.5 in N,N-dimethylacetamide (DMAC) at 140 °C for 3 days. Both 1 and 2 are stable in air for 24 h (Figures S1 and S2, Supporting Information) and insoluble in water and common organic solvents. The phase purities of the asmade samples 1 and 2 were confirmed by PXRD patterns. When changing the solvent to water or DMF or DEF, only powder products with unknown phase were isolated. This suggests that the solvent of DMAC plays a crucial role for the assembly of 1 and 2. Varying the molar ratio of H3btc, Hdmtrz, and Zn(II) salt, PXRD patterns revealed impurity of the bulk samples. The structural difference of 1 and 2 should be related to the different effects of anions during the assembly.6062 IR spectra of 1 and 2 show characteristic bands of dmtrz around 2935 (C—H stretching of CH3 group) and 1410 (CdN stretching of triazole group) and one for btc around 1625 cm1, indicating the presence of both ligands in the products. TGA of 1 (Figure S3) shows a continuous weight loss with the increase of temperature, suggesting low thermal stability of 1 after the release of coordinated water. For 2, the framework is stable up to 150 °C. Structural Description. {Zn7(btc)4(dmtrz)2(H2O)5}n (1). The asymmetric unit of 1 consists of seven crystallographically independent Zn(II) ions, four btc ligands, two dmtrz ligands, and five coordinated water molecules (Figure S4). All dmtrz ligands show uniform μ1,2,4-bridging modes in 1, while four btc ligands exhibit two kinds of coordination modes (modes I and II, Scheme 2). Among the seven Zn(II) atoms, Zn(1)Zn(5) and Zn(7) are all in the tetrahedral coordination geometry. Zn(1)Zn(4) centers 2812
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Scheme 2. Coordination Modes of btc Ligand in 1 and 2
Figure 2. 2 2 2 supercell of 1 showing the wormlike pore structures with van der Waals surfaces (blue, toward the pore; gray, toward the framework).
Figure 1. Nodal modes and network of 1: (a) Paddle-wheel unit of [Zn(O2C)2(dmtrz)] showing a 5-connected node; (b) paddle-wheel unit of [Zn(O2C)3(H2O)4] showing a 3-connected node; (c) four coordinated Zn(7) showing a 3-connected node; (d) 3-connected btc ligand; (e) network of 1.
are tetrahedrally coordinated by three oxygen atoms from btc ligands and one nitrogen atom from dmtrz units. Zn(5) is coordinated by four oxygen atoms (three from btc ligands and one coordinated water (O29W)). Zn(7) is tetrahedrally coordinated by one oxygen atom from monodentate carboxylate, one coordinated water (O(25W)) and N(3) and N(6) from dmtrz units. Zn(6) has a distorted octahedral coordination geometry by three carboxylate oxygen atoms from btc ligands and three coordinated water molecules. The average ZnO and ZnN distances (Table S1 for details) are 1.983 and 2.012 Å, respectively. In structure 1, a triaozle-carboxylate shared paddle-wheel [Zn2(O2C)2(NN)] SBU is observed (Figure 1a), in which the dmtrz ligand connects two Zn(II) ions in μ1,2-mode with two bidentate coordinated carboxylate groups. This SBU is further connected by two monodentate carboxylate groups from btc ligands, generating an asymmetric 5-connected node. Considering the paddle-wheel unit of [Zn2(O2C)3], the btc ligand, and
Zn(6) as 3-connected nodes (Figure 1bd), 1 can be simplified as a (3,5)-connected network (Figure 1e). The solvent accessible volume per unit cell of 1 is estimated by PLATON to be 62.3%. In order to well present the pore channels of 1 based on multiple nodes, the structure is visualized with a van der Waals surface, which shows interesting cross-linked wormlike channels (Figure 2). {[Zn6(btc)4(dmtrz)3] 3 3H3O 3 2H2O}n (2). The asymmetric unit of 2 consists of six crystallographically independent Zn(II) ions, four btc ligands, three dmtrz ligands, and three hydrated protons (Figure S5). All the dmtrz ligands in 2 are in μ1,2,4bridging modes. Three of the four btc ligands exhibit mode-I coordination mode, and all three carboxylate groups of the other btc ligand are monocoordinated with Zn(II) ions (mode-III, Scheme 2). The six Zn(II) atoms are all in the tetrahedral coordination geometry. Zn(1) to Zn(3) centers are coordinated by three oxygen atoms from btc ligands and one nitrogen atom from dmtrz units; Zn(4) to Zn(6) centers are coordinated by two oxygen atoms from btc ligands and two nitrogen atoms from dmtrz ligands. The average ZnO and ZnN distances (Table S1 for details) are 1.957 and 2.012 Å, respectively. In structure 2, besides the existence of [Zn2(O2C)2(NN)] SBU (Figure 3a), a new triazole-carboxylate shared paddle-wheel [Zn2(O2C)(NN)2] SBU (Figure 3b) is observed, in which two dmtrz ligands connect two Zn(II) ions in a μ1,2-mode with one carboxylate group. Considering both paddle-wheel units as 5-connected nodes, Zn(3) and Zn(6) ions as two 4-connected nodes, and btc ligands as 3-connected nodes (Figure 3ce), 2 can be simplified as a (3,4,5)-connected network (Figure 3f). The solvent accessible volume per unit cell of 2 is calculated by PLATON to be 55.9% after theoretically removing the hydrated protons and lattice water. The van der Waals surface of 2 (Figure 4) indicates that the pore structures are also cross-linked wormlike channels. Triazole-carboxylate Shared Paddle-wheel Units. Water was mainly used as the solvent in synthesis of MOFs based on mixed triazole and carboxylate ligands.4850,63 Under this condition, 2813
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Scheme 3. View of Assembly Mechanism of Triazole-carboxylate Shared Paddle-Wheel Units of [Zn(O2C)2(NN)] and [Zn(O2C)(NN)2]
Figure 3. Nodal modes and network of 2: (a) paddle-wheel unit of [Zn(O2C)2(dmtrz)] as a 5-connected node; (b) paddle-wheel unit of [Zn(O2C)(dmtrz)2] as a 5-connected node; (c and d) four coordinated Zn(5) and Zn(6) as two 4-connected nodes; (e) btc ligand as the 3-connected node; (f) network of 2.
Figure 4. 2 2 2 supercell of 2 showing the wormlike pore structures with van der Waals surfaces (blue, toward the pore; gray, toward the framework).
pillar-layer structures were generally isolated, in which the [M2(trz)2] SBU usually generates dense layer structures and dicarboxylate or tricarboxylate ligands serve as pillars. In this work,
amides (DMF, DEF, DMAC) were used as the solvent and DMAC is the proper solvent for the generation of crystalline structure 1 and 2 based on the triazole-carboxylate shared paddle-wheel units of [Zn2(O2C)2(NN)] and [Zn2(O2C)(NN)2]. It is also worth noting that after many trials via changing the zinc salts, solvent, temperature, and molar ratio in the reaction system, we failed to obtain novel structures based on the special units. However, novel porous MOFs based on them can be isolated after replacing the H3btc by other carboxylate ligands under certain conditions, which we will report later. Therefore, the assembly of triazole-carboxylate shared paddle-wheel units should be related to the kind of solvents, and these special SBUs could also be adopted to construct other structures with different carboxylate ligands. The dihedral angle of the adjacent [Zn2(O2C)] plane in traditional paddle-wheel [M2(O2C)4] and [Zn2(O2C)3] SBUs is about 90° and 120°, respectively (Figure S6). By replacing one of the carboxylate groups in [Zn2(O2C)3] SBUs by a μ1,2connected triazole ligand, the angle slightly decreases to be about 110° in the [Zn2(O2C)2(NN)] SBU because of the bulk rigid geometry of the triazole group (Figure S6). Meanwhile, the other two dihedral angles are about 120 and 130°. In the [Zn2(O2C)(NN)2] SBU, the dihedral angle of the adjacent [Zn2(NN)] plane is about 124° (Figure S6), which is similar to that of the bent [M2(trz)2] SBU. The other two dihedral angles are about 126 and 110°. Based on the above analyses, the assembly process is speculated to be as follows (Scheme 3): (i) Aggression to coordination unsaturated metal sites. As mentioned above, the [M2(trz)2] SBU has a possibility to form a bent unit with the dihedral angle approximately 120°, which offers an appropriate steric compatibility for the aggression of one carboxylate group. In the unit of [Zn2(O2C)(NN)2], the dihedral angle of the adjacent [Zn2(NN)] plane is 124°, suggesting the possibility of this process. (ii) Substitution process. The paddle-wheel [Zn2(O2C)3] SBU normally contained two or more coordinated water molecules on one of the metal ions.11 The substitution process can easily be carried out under amide conditions when there exists a strong coordination ligand of triazole, generating a [Zn2(O2C)2(NN)] SBU with one-step substitution and [Zn2(O2C)(NN)2] with secondary substitution. Similarly, the substitution process can also start from the product of process i. (iii) The above two processes, which might be carried out independently or concurrently, can only be performed under the proper assembly environment, for example DMAC solvent. 2814
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’ ASSOCIATED CONTENT
bS
Supporting Information. Tables of selected bond lengths and angles of 1 and 2, tables of the selectivity of some MOFs and other microporous materials, and figures showing PXRD data, TGA data, adsoprtion data, and structures. This material is available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected]. Telephone: þ86 21 65642261. Fax: þ86 21 65643925. Figure 5. Single component gas (CO2, N2, at 298 K) adsorption isotherms of 1 and 2 carried out on an IGA apparatus.
Sorption Properties. To examine the adsorption ability of 1 and 2, single-component sorption of CO 2 and N 2 was carried out on an IGA gravimetrical adsorption apparatus at 298 K, and the adsorption isotherms are depicted in Figure 5. 1 degassed at 323 K shows adsorption amounts of 21.4 mg/g (0.49 mmol/g) and 1.8 mg/g (0.06 mmol/g) for CO 2 and N 2 , respectively. The moderate adsorption amounts are ascribed to occupation of coordinated water molecules, which cannot be totally removed without losing the framework integrity. For 2, the uptake of CO2 increases quickly at low pressure and reaches 18.8 mg/g (0.43 mmol/g) at 100 mbar. With further increasing the pressure, the sorption amount achieves 91.9 mg/g (2.09 mmol/g) at 1000 mbar. Virial analyses of the CO2 adsorption isotherms measured at 298 and 288 K illustrate medium CO2 binding ability of 2 (Figure S7). The enthalpy at zero coverage of 2 is calculated to be 22.7 kJ/mol, which is higher than the liquefaction enthalpy of CO2 (17 kJ/ mol) but lower than those of most MOFs with exposed active sites,6467 suggesting the lower energy requirement in the reactivation process. It is noted that there is no significant N2 uptake at low pressure, only about 0.9 mg/g (0.03 mmol/g) at 100 mbar, which then quickly climbs up to 13.4 mg/g (0.48 mmol/g) at 310 mbar and reaches 18.7 mmol/g (0.67 mmol/g) at 1000 mbar. This one-step transition of sorption can be ascribed to the further fixation of N2 on different sites of the wormlike pore structures.68 The adsorption selectivity for CO2 over N2 was then calculated by the initial slope of the gas uptake amounts (Figure S8).64 The slope ratio (CO2/N2) is calculated to be about 21, which is comparable to that of HKUST-1, H3[(Cu4Cl3)(BTTri)8], and en-H3[(Cu4Cl3)(BTTri)8] (Table S2), indicating a good selectivity toward CO2 over N2 at low pressure.
’ CONCLUSION Two novel porous MOFs {Zn7(btc)4(dmtrz)2(H2O)5}n (1) and {[Zn6(btc)4(dmtrz)3] 3 3H3O 3 2H2O}n (2) have been successfully synthesized, in which triazole-carboxylate shared paddle-wheel units of [Zn2(O2C)2(NN)] and [Zn2(O2C)(NN)2] are observed. The solvent plays an important role for the assembly of such special SBUs. It can be projected that more functional porous frameworks could be constructed based on them. Gas adsorption study suggests that 2 is a potential microporous material for adsorptive separation of CO2 over N2.
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