Porous MetalâOrganic Frameworks with Multiple Cages Based on

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Zeolite-Like Metal–Organic Frameworks in Diversity Based on Tetrazolate Ligands: Synthesis, Structures, Photoluminescence, and Gas Adsorption Properties Tien-Wen Tseng, Tzuoo-Tsair Luo, She-Yu Chen, Chong-Cheng Su, Kai-Ming Chi, and Kuang-Lieh Lu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg3009249 • Publication Date (Web): 21 Nov 2012 Downloaded from http://pubs.acs.org on November 22, 2012

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Crystal Growth & Design

Porous Metal–Organic Frameworks with Multiple Cages Based on Tetrazolate Ligands: Synthesis, Structures, Photoluminescence, and Gas Adsorption Properties Tien-Wen Tseng,*,† Tzuoo-Tsair Luo,‡ She-Yu Chen,‡,§ Chong-Cheng Su,†,‡ Kai-Ming Chi,*,§ and Kuang-Lieh Lu*,‡ †

Department of Chemical Engineering, National Taipei University of Technology, Taipei 106, Taiwan, ‡Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan, and §Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi 621, Taiwan

ABSTRACT: Three tetrazolate-based coordination polymers [Mn(TzA)(H2O)2]n (1, H2TzA = 1H-tetrazole-5-acetic acid), {[Cd5(MTz)9]·OH}n (2, MTz = 5-methyltetrazolate), and [Cd3(MTz)3Cl3]n (3) were synthesized via the reactions of a tetrazole ligand H2TzA with metal ions under hydrothermal conditions. During the formation of 2 and 3, Cd(II) ions were coordinated by MTz−, which was generated as the result of the in situ decarboxylation of the H2TzA ligand. Single-crystal X-ray diffraction analyses revealed that 1 possessed an infinite 2D layer structure with a µ 3-TzA2− moiety, forming a 44-sql topology, and the 2D sheets were further hydrogen-bonded to form a 3D framework. Compound 2 had a 3D porous framework with a 49·66-acs topology. Compound 3 adopted a 3D porous framework with a body-centered cubic (bcu) topology, which was comprised of 48-membered (Cd24Cl24) rings, and it demonstrated a moderate adsorption of H2 over N2 as a result of its limited window size. The solid-state luminescent properties of complexes 2−3 and the corresponding HMTz molecule were also investigated.

Introduction Porous materials such as zeolites, coordination polymers, or metal–organic frameworks (MOFs) are cornerstone industrial chemicals that are utilized in gas storage/separation,1-3 and catalysis.4 Coordination polymers with extra-large porosity have been subjects of intense interest, in terms of combining the highly desirable properties of both zeolites and MOFs, such as crystallinity, high porosity, high surface area, and thermal/chemical stability.5-9 Extensive investigations have demonstrated that the metal ions, the geometries, the coordination sites of organic ligands play vital roles in directing the final structures that are formed via selfassembly processes.10-11 It is well-acknowledged that the tetrazolate ligands used as a tether or a molecular tecton, which possess the distal nitrogen atoms with versatile binding modes, result in the formation of a diversity of porous frameworks with permanent porosities.12-14 It is well known that a ligand containing a tetrazolate moiety and a carboxylate group can function as a precursor of a number of interesting MOFs,15-17 or zeolitic tetrazolate framework (ZTF).18 However, only few MOFs based on 1H-tetrazole-5acetic acid (H2TzA) have been prepared to date.19 As part of our ongoing efforts in exploring functional crystalline materials,21 we report herein on the synthesis and crystal structures of three MOFs based on the utilization of the H2TzA ligand. This work is noteworthy for several reasons: (i) compounds {[Cd5(MTz)9]·OH}n (2), and [Cd3(MTz)3Cl3]n (3) are constructed from the Mtz− ligand, generated in situ from the decarboxylation of H2TzA, which is observed for the first time; (ii) compound 2 with a 49·66-acs topology; (iii) complex 3 displays a bodycentered cubic topology with multiple cages and a high degree of thermal stability; (iv) whether the product is 2 or 3 depends on the amount of ancillary Cl− ligand, which exhibits a vital structuredirecting effect; (v) 2−3 exhibits a moderate fluorescence in the solid state. Experimental Section General Remarks. All reagents were purchased commercially and used as received without further purification. The thermogravimetric analysis (TGA) was performed under nitrogen with a Perkin-Elmer Pyris 6 analyzer. The IR spectra were recorded in the 4000−400 cm−1 region using KBr pellets on a Perkin-Elmer

Paragon 1000 spectrometer. Elemental analyses were determined using a Perkin-Elmer 2400 elemental analyzer. The powder X-ray diffraction patterns (PXRD) were recorded on a MPD Philips Analytical diffractometer at 40 kV, 30 mA for Cu Kα (λ = 1.5406 Å). The energy-dispersive X-ray (EDX) spectra are carried out on an OXFORD X-MAX spectroscopy. The solid-state photoluminescent measurements were recorded on a Hitachi F4500 spectrometer. The gas sorption experiments were measured with an ASAP 2020 gas adsorption instrument. [Mn(TzA)(H2O)2]n (1). A mixture of 1H-tetrazole-5-acetic acid (H2TzA, 81.0 mg, 0.631 mmol), NaN3 (101.8 mg, 1.56 mmol) and MnCl2·4H2O (80.8 mg, 0.408 mmol) in 3.0 mL water was sealed in a Teflon-lined Parr acid digestion autoclave and heated at 180 °C for 72 h. After slowly cooling the solution to room temperature at a rate of about 2 °C/h, the colorless crystals of compound 1 were separated by filtration, washed with water and ethanol, and dried in air. Yield: 77.2% (68.4 mg, 0.315 mmol) based on Mn(II). IR data (KBr, cm−1): 3559(s), 3420(s), 3273(s), 3030(s), 1676(m), 1610(m), 1542(m), 1488(w), 1439(m), 1408(m), 1390(m), 1280(w), 1213(w), 1182(w), 1140(w), 1103(w), 1055(w), 951(w), 835(w), 738(m). UV-Vis (DMSO): λmax = 268 (π−π*), 445 (MLCT), 622, 668 nm. Elemental anal. Calcd for C3H6N4O4Mn: C, 16.60; H, 2.79; N, 25.81%. Found: C, 16.73; H, 2.82; N, 25.12%. {[Cd5(MTz)9]·OH}n (2). A mixture of 1H-tetrazole-5-acetic acid (0.353 mmol) acid (H2TzA, 128.3 mg, 1.00 mmol), CdCl2·4H2O (90.1 mg), and 3.0 mL distilled water was sealed in a 23.0 mL Teflon-lined Parr acid digestion autoclave and heated hydrothermally at 180 °C for 48 h. After slowly cooling down to room temperature at about 2 ℃/h, colorless crystals of 2 were isolated by filtration, washed with water and ethanol, and dried in air. Yield: 27.3 mg (0.0206 mmol), 29.2% based on Cd(II). Alternatively, using Cd(NO3)2·4H2O instead of CdCl2·2.5H2O in water under similar reaction conditions also afforded compound 2 in high yield. IR data (KBr, cm−1): 3622(s), 3500(s), 2314(w), 2186(w), 1643(m), 1488(m), 1444(w), 1372(m), 1233(m), 1172(m), 1089(m), 1045(m), 701(m). Elemental anal. Calcd for C18H28N36OCd5: C, 16.30; H, 2.13; N, 38.01%. Found: C, 16.53;

ACS Paragon Plus Environment


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Table 1. Crystal Data and Structure Refinements for Compounds 1–3 compound 1 empirical formula C3H6N4O4Mn 217.06 Mw crystal system orthorhombic space group Pca21 a (Å) 9.7285(3) b (Å) 8.4433(2) c (Å) 8.4433(2) α (deg) 90 90 β (deg) γ (deg) 90 693.54(3) V (Å3) Z 4 T (K) 293(2) 0.71073 λ (Å) 2.079 Dcalc (g·cm−3) 1.884 µ (mm−1) 436 F000 GOF 0.965 0.0220 R1a (I > 2σ (I)) 0.0467 wR2b (I > 2σ (I)) 0.0254 R1a (all data) wR2b (all data) 0.0471 a

2 C18H28N36OCd5 1326.76 trigonal P−31c 13.0959(19) 13.0959(19) 13.650(3) 90 90 120 2027.4(6) 4 293(2) 0.71073 2.173 2.650 1272 1.086 0.0953 0.2770 0.1272 0.2961

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3 C6H9Cl3N12Cd3 692.8 tetragonal I−42m 22.2366(2) 22.2366(2) 18.6742(3) 90 90 90 9233.76(19) 16 293(2) 0.71073 1.993 3.099 5184 1.101 0.0466 0.1239 0.0645 0.1327

R1 = Σ∥Fo| − |Fc∥/Σ|Fo|; bwR2 = {Σ[w(Fo2 − Fc2)2]/Σ[ w(Fo2)2]}1/2.

H, 1.95; N, 38.18%. [Cd3(MTz)3Cl3]n (3). Pale yellow crystals of compound 3 were prepared by the reaction of CdCl2·4H2O (176.3 mg, 0.690 mmol) with H2TzA (67.8 mg, 0.528 mmol) under similar reaction conditions, except that the molar ratio of the Cd(II) ion to the H2TzA ligand was set to 1.31:1. Yield: 40.9 mg (0.0590 mmol), 33.5% based on H2TzA. Elemental anal. Calcd for C6H9Cl3N12Cd3: C, 10.40; H, 1.31; N, 24.26%. Found: C, 10.81; H, 1.45; N 23.67%. IR data (KBr, cm−1): 3600(s), 3456(s), 2944(w), 2408(w), 2308(w), 2192(w), 1626(m), 1560(m), 1488(s), 1444(w), 1372(s), 1266(m), 1161(s), 1100(w), 1050(m), 983(w), 741(w), 710(m), 695(s). Crystal Structure Determination. Single-crystal X-ray data were collected using a Nonius Kappa CCD diffractometer, equipped with Mo Kα radiation (λ = 0.71073 Å). Intensity data were collected at 293(2) K. All the structures were solved using direct methods. All the hydrogen atoms of the ligands were placed in calculated positions with isotropic thermal parameters and included in the structure factor calculations in the final stage of fullmatrix least-squares refinement. All calculations were performed using the SHELX-97 program packages.22 The C–H hydrogen atoms were assigned by geometrical calculation and refined as a riding model while the O–H hydrogen atoms were located from the difference Fourier maps. The crystallographic data of compounds 1–3 were summarized in Table 1, and the selected bond lengths and angles were listed in Table 2. Gas Sorption Measurements of Compound 3. The adsorption isotherms of H2 and N2 of 3 were determined at 77 K. While CO2 gas adsorption isotherms were carried out at 273 K. The adsorption isotherms were collected under a pressure in the range from 10−4 to 850 mmHg. The cryogenic temperature 77 K was controlled by liquid nitrogen. A freshly prepared sample of 3 was pretreated at about 140 °C under high vacuum (less than 10−6 mbar) for 12 h. Results and Discussion Synthesis of Compounds 1− −3. The self-assembly of MnCl2·4H2O with 1H-tetrazole-5-acetic acid (H2TzA), NaN3 in water under hydrothermal conditions led to the formation of compound [Mn(TzA)(H2O)2]n (1, Scheme 1). Alternatively, the treatment of CdCl2·4H2O with H2TzA under similar reaction condi-

tions afforded compounds {[Cd5(MTz)9]·OH}n (2) and [Cd3(MTz)3Cl3]n (3). It is noteworthy that, during the synthesis of compounds 2 and 3, a new 5-methyltetrazolate (MTz−) moiety was generated from the TzA2− ligand via in situ decarboxylation (Scheme 1). This type of decarboxylation is very different from other cases.20 In general, carboxylate groups that are directly attached to an aromatic ring can undergo in situ decarboxylation.28 To the best of our knowledge, a decarboxylation transformation involving such a H2TzA ligand is reported here for the first time. Effective Strategy for the Synthesis of Compounds 2 and 3. Because compounds 2 and 3 were synthesized under very similar reaction conditions only except for the metal/ligand molar ratio, the determination of optimal reaction conditions is critical. The reactions were carried out by following the above-mentioned procedure in detail and relevant experimental data are given in Table S2 in the Supporting Information. Interestingly, the higher TzA2−/Cd2+ ratio prefers the formation of compound 2, the lower favors compound 3. In addition, when the amount of CdCl2 is increased in solution, the more Cl− ions can participate in the reactions, the more crystals of compound 3 were obtained. This observations verify that compound 2 tends to form in higher yield using Cd(NO3)2 as a starting material instead of CdCl2. On the other hand, the formation of compound 3 favors an environment that contains more Cl− ions (Scheme 2). Crystal Structure of [Mn(TzA)(H2O)2]n (1): A single-crystal X-ray diffraction analysis revealed that compound 1 had a 2D framework and crystallized in the orthorhombic Pca21 space group. The MnII atom is coordinated in a distorted MnN2O4 octahedral geometry by two N atoms (N1, N4) and two O atoms (O1, O2) from two different TzA2− anions, and is completed by two water O atoms (O3, O4) (Figure 1a). Each TzA2− ligand acts as a tridentate linker to bridge to three Mn(H2O)2 cores using O1 atom from one carboxylate group, and the N1 atom from the tetrazolate motif. The Mn−O bond distance is 2.190(1) Å, the Mn−N bond distance is 2.231(2) Å. The µ 2-carboxylate group exhibits in a syn-anti bridging mode and linked to the adjacent Mn atom (Mn−O2 = 2.140(1) Å). The fact that compound 1 contains a carboxylate group, as evidenced by the IR spectrum, which shows strong peaks at 1676, 1610 cm−1 (Figure S31). The µ 3-TzA2− ligand (as shown in Chart 1, mode IV) is bridged by its N4 atom


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Chart 1. The available Coordination Modes of the TzA2− Ligand

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Scheme 1. Synthesis of Compounds 1−3

[Mn(TzA)(H2O)2]n (1)

(I)

(II)

(III)

{[Cd5(MTz)9]·OH}n (2)

− CO2

N

N

N NH (IV)

(V)

[Cd3(MTz)3Cl3]n (3)

(VI)

Chart 2. Coordination Modes of 5-Methyltetrazolate (Mtz−) Ligand

Scheme 2. The Anion Effect on the Formation of Compounds 2 and 3 Cd(NO3)2

(VIII)

(VII)

{[Cd5(MTz)9]·OH}n (2)

CdCl2

Table 2. Selected Bond Lengths [Å] and Angles [°] for 1–3 1

[Cd3(MTz)3Cl3]n (3)

a

Mn(1)−O(2)

2.140(1)

Mn(1)−O(4)

2.224(4)

O(1)−Mn(1)−N(4)

177.86(7)

Mn(1)−O(3)

2.153(3)

Mn(1)−N(1)

2.2313(15)

O(2)−Mn(1)−N(1)

174.84(6)

Mn(1)−O(1)

2.190(1)

Mn(1)−N(4)

2.2647(17)

O(3)−Mn(1)−N(1)

91.61(10)

O(3)−Mn(1)−O(4)

174.22(9)

N(1)−Mn(1)−N(4)

96.40(6)

O(1)−Mn(1)−N(1)

81.56(5)

O(1)−Mn(1)−O(4)

93.14(9)

O(2)−Mn(1)−N(4)

88.56(6)

Cd(2)−N(2)

2.36(1)

N(2)#2−Cd(2)−N(4)#2

90.6(5)

N(2)#2−Cd(2)−N(4)

178.8(5)

Cd(1)−N(3)

2.34(1)

N(3)−Cd(1)−N(5)

91.8(5)

N(5)#1−Cd(1)−N(1)#1

88.5(5)

Cd(1)−N(5)

2.36(1)

N(3)#1−Cd(1)−N(5)

88.2(5)

N(2)−Cd(2)−N(4)#2

90.4(5)

Cd(1)− N(1)

2.37(1)

Cd(2)−N(4)

2.41(2)

N(5)#1−Cd(1)−N(1)

91.5(5)

N(3)#1−Cd(1)−N(3)

180.0 (1) 86.7(2)

2

3 Cd(1)−N(5)

2.317(9)

Cd(2)−Cl(3)

2.573(3)

N(10)−Cd(1)−Cl(2)

Cd(1)−N(10)

2.371(9)

Cd(2)−Cl(1)

2.621(3)

N(12)−Cd(1)−Cl(2)

86.8(3)

Cd(1)−N(12)

2.436(9)

Cd(3)−N(11)

2.28(1)

N(2)−Cd(1)−Cl(2)

173.3(2)

Cd(1)−N(2)

2.440(9)

Cd(3)−N(7)#3

2.38(1)

Cl(1)−Cd(1)−Cl(2)

101.4(1)

Cd(1)−Cl(1)

2.544(3)

Cd(3)−N(3)

2.380(9)

N(9)−Cd(2)−N(1)

92.7(3)

Cd(1)−Cl(2)

2.560(3)

Cd(3)−N(6)

2.49(1)

N(4)#2−Cd(2)−Cl(3)

86.3(2)

Cd(2)−N(9)

2.37(1)

Cd(3)−Cl(4)

2.541(3)

N(9)−Cd(2)−Cl(1)

91.6(2)

Cd(2)−N(1)

2.38(1)

Cd(3)−Cl(3)#4

2.539(3)

N(8)#1−Cd(2)−Cl(1)

175.2(2)

N(4)−Cd(2)#4

2.391(9)

N(10)−Cd(1)−N(2)

88.5(3)

N(4)#2−Cd(2)−Cl(1)

92.0(2)

N(8)−Cd(2)#6

2.389(9)

N(10)−Cd(1)−N(12)

82.7(3)

N(5)−Cd(1)−N(2)

91.1(3)

N(11)−Cd(3)−N(6)

86.9(3)

N(11)−Cd(3)−N(6)

86.9(3)

N(3)−Cd(3)−Cl(4)

170.9(3)

N(11)-Cd(3)-Cl(4)

91.2(3)

N(6)−Cd(3)−Cl(4)

87.8(2)

N(11)−Cd(3)−N(3)

92.0(4)

a

Symmetry transformations used to generate equivalent atoms: for 2: #1 -x+2,-y+1, -z ; #2 -x+y+2, -x+2, z; for 3: #1 -y+1/2, -x+1/2, z+1/2 ; #2 -y+1/2, x1/2, z+1/2 ; #3 -x+1, y, -z ; #4 y+1/2, -x+1/2, -z+1/2; #6 -y+1/2, -x+1/2, z-1/2.

to connect the near MnII center (Mn−N4 = 2.265(2) Å and extended to form a 2D square-grid sheet (Figure 1b).Compound 1 features an interesting layer structure with a 44-sql topology, which is composed of the tetranuclear [Mn4(TzA)2] fragment. The Mn(II) ions are treated as a 4-connected node. Each TzA2− anion, which is coordinated to three Cd(II) centers, can be regarded as a three-bridged linker. Meanwhile, these mildly un-

dulating 2D sheets are further packed together in an alternative ABAB manner to form a 3D structure (Figure 1c). There are hydrogen-bonding interactions among adjacent layers between coordinated water molecules and carboxylate oxygen atoms and tetrazolate nitrogen atoms of the TzA2− ligands (Table S1). The separate distance between the adjacent tetrazolate rings is 3.56 Å,



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(a)

(b)

(d)

Page 4 of 9 (c)

(e)

Figure 1. (a) ORTEP representation of 1, showing the local environment of the MnII center. (b) A 2D grid sheet with 44-sql topology in the ab-plane (dark green, Mn; blue, N; red, O; grey, C). (c) Projective view of the sheets staggered in an ABAB manner along the c axis. (d) Hydrogen-bonded to construct the 3D MOF. (e) A packing diagram reveals the π–π interactions in dotted lines.

(b)

(a)

(c)

(d)

Figure 2. (a) ORTEP drawing of 2. (b) The environment of Cd2 centers coordinated by four µ 3-MTz− and two µ 4-MTz− ligands. (c) The environment of the Cd1 center coordinated by three µ 3- and three µ 4-MTz−. (d) Schematic presentation of the Cd2-network with lonsdaleite (lon) topology (green/Cd1 and prune/Cd2), which is resulted from the connection of the trigonal prism [Cd5(MTz)9]+.

showing a strong π–π stacking interaction (Figure 1e). Crystal Structure of {[Cd5(MTz)9]·OH}n (2): A single crystal X-ray diffraction analysis revealed that compound 2 crystallized in the trigonal space group P−31c and manifested two kinds of octahedral environments of CdII atoms (Figure 2a). The Cd1 center is coordinated with six nitrogen atoms (Figure 2b), four of which arise from four independent µ 3-MTz− anions and the other two from two distinct µ 4-MTz− ligands. The Cd2 atom is also coordinated with six nitrogen atoms, among which three are from independent µ 3-MTz− ligands and the other from three distinct µ 4MTz− ligands (Figure 2c). Remarkably, the MTz− ligands are bridged in µ 3- and µ 4-connecting mode. The µ 3-MTz− ligand, lying on the basal side of the prism, is coordinated to two Cd1 atoms and one Cd2 atom (Figure 2d; Chart 2, mode VI). The µ 4MTz− ligand, located on the lateral side of the prism, is linked to two Cd1 atoms and two Cd2 atoms (mode VII). The mean bond

length of Cd1−N is 2.35 Å, and the N−Cd−N bite angles fall in the range of 88.2−91.8°. All of the Cd–N bond lengths are comparable for reported CdII tetrazolate complexes.23 It should be noted that each horizontal edge of [Cd5(MTz)9]+ (Figure 2d) is connected by a µ 3-MTz− group. The axial edge is bridged by µ 4-MTz−, which is coordinated to two Cd1 and two Cd2 atoms. Each methyl moiety of the MTz− ligand is directed vertically into the edge of the [Cd5(MTz)9]+ prism. If treating the Cd1 atom as a node and the MTz− ligand as a linker, as shown in Figure 3a, the Cd1-network with an interesting Kagomé topology is apparent.24 Moreover, if the Cd2 center is regarded as a node and the MTz− ligand as a linker (Figure 3b, S6), a hexagonal Cd2-network with a lon-topology is formed.25 In addition, topological analyses indicated that the overall network of compound 2 possesses a (49·66)-acs framework (Figure 3c).26


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Crystal Growth & Design (a)

(c)

(b)

Figure 3. (a) Schematic representation of the Cd1-network with Kagomé skeleton constructed with the Cd1 atoms as nodes and the MTz− ligands as linkers viewed along the c axis. (b) Perspective view of of the Cd2-network with 66-lon topology viewed along the a axis (c) The framework 2 with (49.66)-acs topology (pale blue/Cd1, and prune/Cd2, blue line/ligand). The included hydroxide anions are omitted for clarity.

(a)

(b)

Figure 4. (a) A 1D channel of 6.09 × 6.09 Å2 (highlighted in yellow) along the a axis. (b) A space-filling model of 2 shows OH− anions (highlighted in red) that are included within the channels viewed along the c axis.

(a)

(b)

Figure 5. (a) ORTEP drawing of 3 reveals three independent Cd centers, which are bridged by µ 2-Cl− and µ 4-MTz− anions to form a trinuclear cluster unit. (b) Showing a 48-membered ring, which is connected by the CdII cluster.

(a)

(b)

(c)

Figure 6. (a) A simplified arrangement of the 48-menbered rings of 3. (b) Presentation of the coordination modes of the µ 4-MTz ligands (CdII in dark green, linkers in pale green). (c) Presentation of the linking to the adjacent rings, which are bridged via the µ 4-MTz ligands in two kinds of modes.

There are large 1D hexagonal channels with a Cd-to-Cd cross section of 6.09 × 6.09 Å2, as shown in Figure 4a. Because the [Cd5(MTz)9]+ building unit is employed to construct the tubular architecture, the framework skeleton of 2 shows cationic characteristics. The hydroxide anions were encapsulated within the tubular structure as counter ions to achieve charge balance. The EDX analysis of 2 (Figure S23) reflects the fact that hydroxide anions are included within the channels (Figure 4b). Crystal Structure of [Cd3(MTz)3Cl3]n (3): A single-crystal Xray diffraction analysis revealed that 3 crystallized in the tetragonal space group I−42m and possesses a trinuclear Cd3-cluster

building unit (Figure 5a) constructed from three independent CdII metal centers, which are bridged by µ 2-Cl− and µ 4-MTz− anions. Each CdII atom is coordinated by two µ 2-Cl anions in a cis-form and four nitrogen atoms from four distinct µ 4-MTz ligands, exhibiting a distorted octahedral geometry. The average Cd−N bond distances are 2.385 Å and the Cd−Cl bond lengths are in the range of 2.541 to 2.621 Å. The bond angles of Cl(3)−Cd(3)−Cl(4) and Cl(3)−Cd(3)−N(11) are 102.43° and 100.93°, respectively. It is noteworthy that the coordination environments of Cd1 and Cd3 centers are nearly the same and symmetrical. The Cd3-clusters



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(a)

(b)

(c)

(d)

(e)

(f)

Figure 7. The architectures of 3: (a) polyhedral representation of wheel-shaped cages; (b) the framework skeleton ; (c) the two kinds of pores; (d) the large pore with dimensitions of 10.32 × 10.32 × 15.04 Å3 highlighted as a yellow sphere; (e) the µ 2-Cl atoms and methyl motifs are directed toward the small pore (pore in yellow, Cl in pale green, methyl motifs in gray) with dimensitions of 9.32 × 6.58 × 4.09 Å3; (f) a perspective view of pores inside the bcu-type network.

are further linked via the Cl− and MTz− bridging ligands to form a specific 48-membered ring (Cd24Cl24, Figures 5b, S8). The other nitrogen atoms of the MTz−ligands further connect the adjacent Cd24Cl24 rings to produce the 3D architecture with multiple cages (Figures 6, 7 and S10). This framework can be regarded as a body-centered cubic (bcu) network.27 There are different pores within the framework. The size of the large cavity is estimated to be 10.32 × 10.32 × 15.04 Å3. There are eight µ 2-Cl atoms and eight methyl groups of µ 4-MTz− ligands that are orientated toward the voids. The small pore size is 9.32 × 6.58 × 4.09 Å3. To the best of our knowledge, compound 3 is a rare example of a porous MOF that is constructed from such a 48-membered tetraicosanuclear building units.27 Thermal Analyses, X-ray Powder Diffraction, and Photoluminescent Properties. Thermogravimetric analyses (TGA) of 1 indicated that the coordinated water molecules were lost in the range of 120−210 °C (Figure S24). The found 14.9% weight loss is consistent with the calculated value (15.0%). After the loss of the water molecules, the framework began to decompose with a continuous weight loss of 47% up to 400 °C, which could be attributed to the loss of coordinating ligands. Both TGA profiles of 3D frameworks 2 and 3 were also found to show no significant weight loss for temperature of up to 365 °C, suggesting that these compounds are highly thermally stable (Figure S24). The results of X-ay powder diffraction (PXRD) were used to check the purity of 1−3 (Figures S25, S26), and the results showed that all peaks were displayed in the measured patterns at room temperature closely matched those in the simulated patterns. The results of preliminary photoluminescent properties of complexes 2 and 3 were measured in the solid state at room temperature (Figure 8 and S27). The HMTz molecule displayed aweak luminescence in the range of 290~350 nm (Figure S28). Moderate emissions of 423 and 464 nm were found for 2, which were excited at 240 and 338 nm, respectively. The similar moderate emissions of 3 were found at 410 and 466 nm. They are tentatively assigned as originating from the emission wavelengths with the intraligand π−π∗ transition of the MTz− ligand from 2 and 3. This indicates

Figure 8. Emission spectra of 2 exhibited in the solid state at room temperature.

some red-shift and an enhanced intensity of the emissions, which may be ascribed to the chromophore of the tetrazolate groups that are more rigid and conjugated for MOFs 2 and 3, which are compared with the parent HMTz molecule. Gas Adsorption Properties of 3. To evaluate the hydrogen storage efficiency, fresh crystals of 3 were activated by placing them in a vacuum at 140 °C for 12 h, and the hydrogen sorption isotherms were measured from low pressure to 870 mmHg at 77 K. There were different micropores within 3 with sizes of 9−10 Å and 4−5 Å. Its accessible framework free volume was calculated to be 32.7% with PLATON.29 As shown in Figure S29, the moderate hydrogen uptake of sample 3 is up to 0.82 wt% at 77 K and 1 atm, which can be ascribed to the suitable hydrophobic cavity involving the methyl groups. As shown in Figure 9, three different kinds of gas adsorption isotherms were obtained. The results indicate that MOF 3 cannot adsorb significant amount of N2 at 77 K, but can adsorb H2 up to 80 cm3 g−1 (77 K, 1 atm). The uptake of CO2 is 43 cm3 g−1 (273 K, 1 atm). Thus, compound 3 seemingly exhibits a moderate adsorption selectivity for H2 over N2, which can be attributed to the nature of the suitable pore sizes.


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5.

6.

Figure 9. The gas adsorption isotherms of 3 (black, for H2-77K; green, for CO2-273 K; red, for N2-77 K).

Conclusion In summary, a remarkable porous MOF 3, and the key MTz− ligand were generated from the in situ decarboxylation of H2TzA. The MOF 3 adopts a body-centered cubic (bcu) topology with multiple cages and a high thermal stability. In addition, the MOF 2 with a 49·66-acs topology was also obtained under similar conditions except for the presence of NO3− anion instead of Cl−. The counter Cl− anion had a critical influence on the formation of 2 and 3.

7.

8.

Acknowledgement. We are grateful to National Taipei University of Technology, Academia Sinica, and the National Science Council of Taiwan for financial support. Supporting Information: X-ray crystallographic files in CIF format and the figures of 1−3. Tables S1−S2, IR, TGA, photoluminescent properties of 3 and HMTz, and PXRD patterns of 1−3. This material is available free of charge via The Internet at http: //pubs.acs.org. * To whom correspondence should be addressed. Fax: Fax: +886-2-27317117. E-mail: [email protected].

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Synopsis Three 3D MOFs of [Mn(TzA)(H2O)2]n (1), {[Cd5(MTz)9]·OH}n (2), and {[Cd3(MTz)3]·Cl3}n (3) have been synthesized from 1H-tetrazole-5-acetic acid (H2TzA) or the 5-methyltetrazolate (MTz−, which was in situ formed from the decarboxylation of H2TzA) under hydrothermal conditions. The coordination diversity of H2TzA and its derivative Mtz− manifests the versatile bridging modes. The auxiliary coordinated Cl− anion exhibited a profound structure-directing effect on the coordination fashion of metal centers and the linking modes of the MTz− ligand, leading to the target porous MOFs with distinct topologies.

[Mn(TzA)(H2O)2]n (1)

OH

N N N

NH

O

{[Cd5(MTz)9]·OH}n (2)

N N N

NH

[Cd3(MTz)3Cl3]n (3)


Porous MetalâOrganic Frameworks with Multiple Cages Based on

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