A Highly Symmetric Porous Framework with Multi-intersecting Open

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CRYSTAL GROWTH & DESIGN

A Highly Symmetric Porous Framework with Multi-intersecting Open Channels Lin,†,‡

Jiang,†

Zheng-Zhong Fei-Long Lian An-Jian Lan,† and Mao-Chun Hong*,†

Chen,†

Cheng-Yang

Yue,†

Da-Qiang

Yuan,†

2007 VOL. 7, NO. 9 1712-1715

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Graduate School of the Chinese Academy of Sciences, Chinese Academy of Sciences, Fujian, Fuzhou 350002, China, and College of Biology Engineering, Jimei UniVersity, Xiamen 361021, China ReceiVed October 19, 2006; ReVised Manuscript ReceiVed June 5, 2007

ABSTRACT: A porous anionic framework with cubic symmetry and multi-intersecting open channels, {[H2tmdp]3[In6(btc)8]‚ 40H2O}n (1) (tmdp) 4,4′-trimethylene dipiperidine, H3btc)1,3,5-benzenetricarboxylic acid), is reported. Complex 1 crystallizes in the cubic space group I4h3d (a ) b ) c ) 20.3732(8) Å, V ) 8456.2(6) Å3, and Z ) 2). Its cagelike units, In9(btc)11, constitute a large accessible void with 65.4% of the total volume. The cationic guests located in the channels can be exchanged with inorganic ions, such as K+, NH4+, Ca2+, Sr2+, and Ba2+. Introduction The intense pursuit of open framework is motivated by the interest in producing structures with cavities or channels that are expected to find applications in areas such as catalysis,1 adsorption and separation,2 ion-exchange,3 and storage.4 Recently, the research activities in this field have resulted in enormous metal-organic porous solids with structures and properties different from the well-known zeolite frameworks;5,6 however, reports on the metal-organic frameworks with very high symmetry are rarely documented.7 One particularly useful family of ligands that has been used to create high-symmetry frameworks contains multicarboxylate functional groups, such as 1,3,5-benzenetricarboxylic acid (H3btc). The H3btc ligand compound provides high symmetry and rigid conformation with diverse charge and multiconnecting ability, which have been applied in the design of thermally stable porous open frameworks.8-10 Recently, our group have become interested in using indium(III) ions with H3btc to create coordination polymers. Indium ions here are typical of +3 oxidation state and have the ability to adopt MO6,11 MO7,12 or even MO813a coordination numbers13b,c in contrast to traditional divalent transition metals, which are usually four- or six-coordinated. Indium is widely used in several corner-linked MS4 tetrahedral metal-sulfide compounds with large pores and channels known as the supertetrahedra.14 But the porous frameworks constructed from indium(III) and organic ligands are less investigated. Our goal is to explore how the increased valences of metal ions with highly variable coordination numbers have a strong influence on the resulting structures. By employing the strategy that combines both high symmetric carboxylate ligands and promising indium(III) ions, we successfully obtain a highly open framework: {[H2tmdp]3[In6(btc)8]‚40H2O}n (1) (tmdp) 4,4′-trimethylenedipiperidine). Herein, we wish to report its synthesis, structure, ion exchange, and photophysical properties. Experimental Section Materials and Analyses. All reagents were of analytical grade and used as obtained from commercial sources without further purification. * To whom correspondence should be addressed. E-mail: hmc@ fjirsm.ac.cn. Phone: 86-591-83792460. Fax: 86-591-83714946. † Chinese Academy of Sciences. ‡ Jimei University.

IR (KBr pellets) spectra were recorded in the 400-4000 cm-1 range using a Perkin-Elmer Spectrum One FTIR spectrometer. Elemental analyses were carried out on Elementar Vario EL III microanalyzer. Fluorescent data were collected on an Edinburgh FL-FS920 TCSPC system. X-ray powder diffraction (XRD) patterns (Cu KR) were collected in a sealed glass capillary on a XPERT-MPD θ-2θ diffractometer and TG (thermal gravimetric) analysis was performed with a heating rate of 10 °C min-1 using a NETZSCH STA 449C simultaneous TG-DSC instrument. Preparation of {[H2tmdp]3[In6(btc)8]‚40H2O}n (1). A mixture of InCl3‚4H2O (148.0 mg, 0.5mmol), H3btc (105 mg, 0.5mmol), tmdp (210 mg, 1mmol), and H2O (7.0 mL) in a 30 mL Teflon-lined stainless steel vessel was heated at 170 °C for 32 h, and the reaction system was then cooled to room temperature at a rate of 6 °C h-1, giving air-stable yellow cubic crystals of complex 1 with an isolated yield of 70% (120 mg) based on InCl3‚4H2O. Elemental anal. Calcd for 1: C, 35.97; N, 2.27; H, 5.13. Found: C, 35.40; N, 2.27; H, 5.10. IR (KBr, cm-1): 3412 (m, br), 2972 (w), 2928 (w), 1626 (s, sh), 1574 (m), 1541 (m), 1448 (sh), 1375 (vs, sh), 1212 (w), 1104 (w), 1050 (w), 766 (m, sh), and 712 (m, sh). Crystallographic Studies. Intensity data were collected on a Rigaku mercury CCD diffractometer with graphite-monochromated Mo KR (λ ) 0.71073 Å) radiation using the omega scan method at room temperature. The structure was solved with direct methods and refined on F2 with full-matrix least-squares methods using SHELXS-97 and SHELXL-97 programs, respectively.15,16 All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were added in the riding model and refined isotropically with C-H ) 0.93 Å, N-H ) 0.86 Å. The crystallographic data are summarized in Table 1, and the selected bond lengths and bond angles are listed in Table 2. More details on the crystallographic studies as well as atom displacement parameters are given in the Supporting Information.

Results and Discussion Structural Description. The structure of complex 1 is a three-dimensional coordination framework consisting of four independent intersecting channels. Each indium ion in 1 is coordinated by eight oxygen atoms from four btc ligands to form a decahedron motif, which exhibits high coordinating ability of main group elements (Figure 1). This, therefore, defines a three-connecting node within the structure. Each of the three carboxylate arms of btc ligand binds to an indium atom in chelating bidentate mode, thus defining a fourconnecting node. These joints give rise to an In9(btc)11 cagelike unit (Figure 2), in which two parallel btc (basal btc for short) ligands locate at the top and the bottom of the cage, respectively. The basal btc groups together with nine lateral btc groups and

10.1021/cg060732o CCC: $37.00 © 2007 American Chemical Society Published on Web 07/28/2007

Symmetric Porous Framework with Intersecting Open Channels

Crystal Growth & Design, Vol. 7, No. 9, 2007 1713

Table 1. Crystallographic and Structure Refinement Parameters for 1 formula fw cryst syst space group a ) b ) c (Å) V (Å3) F(000) GOF Z dcalcd (g cm-3) T (K) λ(Mo KR) (Å) µ (mm-1) R1 (I > 2σ(I))a wR2 (all data)a

C111H188In6N6O88 3703.59 cubic I-43d 20.3732(8) 8456.2(6) 3788 1.055 2 1.455 293 0.71073 0.902 0.0570 0.1484

a R ) ∑(||F | - |F ||)/∑|F |. wR ) [∑w(F 2 - F 2)2/∑w(F 2)2]1/2. w ) o c o 2 o c o 1/[σ2(Fo2) + (0.0400P)2 + 122.7902P], where P ) (Fo2 + 2Fc2)/3.

Table 2. Selected Bond Distances (Å) and Angles (deg) for 1a In1-O1B In1-O1C In1-O1 In1-O1A In1-O2B In1-O2C In1-O2 O1B-In1-O1C O1B-In1-O1 O1C-In1-O1 O1B-In1-O1A O1C-In1-O1A O1-In1-O1A O1B-In1-O2B O1C-In1-O2B O1-In1-O2B O1A-In1-O2B O1B-In1-O2C O1C-In1-O2C O1-In1-O2C O1A-In1-O2C O2B-In1-O2C O1B-In1-O2 O1C-In1-O2 O1-In1-O2 O1A-In1-O2 O2B-In1-O2 O2C-In1-O2 O1B-In1-O2A O1C-In1-O2A O1-In1-O2A O1A-In1-O2A O2B-In1-O2A O2C-In1-O2A O2-In1-O2A O1B-In1-C1B O1C-In1-C1B O1-In1-C1B O1A-In1-C1B O2B-In1-C1B O2C-In1-C1B O2-In1-C1B O2A-In1-C1B O1B-In1-C1C O1C-In1-C1C O1-In1-C1C

2.155(5) 2.155(5) 2.155(5) 2.155(5) 2.409(5) 2.409(5) 2.409(5) 135.6(3) 98.21(9) 98.21(9) 98.21(9) 98.21(9) 135.6(3) 56.36(18) 87.5(2) 77.95(19) 143.68(17) 87.5(2) 56.36(18) 143.68(17) 77.95(19) 75.7(3) 143.68(17) 77.95(19) 56.36(18) 87.5(2) 128.58(17) 128.58(17) 77.95(19) 143.68(17) 87.5(2) 56.36(18) 128.58(17) 128.58(17) 75.7(3) 28.19(18) 112.4(2) 87.82(19) 122.6(2) 28.16(18) 80.5(2) 144.1(2) 103.61(18) 112.4(2) 28.19(18) 122.6(2)

In1-O2A O1-C1 O2-C1 C2-C3 C2-C3D C2-C1 C3-C2E O1A-In1-C1C O2B-In1-C1C O2C-In1-C1C O2-In1-C1C O2A-In1-C1C C1B-In1-C1C O1B-In1-C1A O1C-In1-C1A O1-In1-C1A O1A-In1-C1A O2B-In1-C1A O2C-In1-C1A O2-In1-C1A O2A-In1-C1A C1B-In1-C1A C1C-In1-C1A O1B-In1-C1 O1C-In1-C1 O1-In1-C1 O1A-In1-C1 O2B-In1-C1 O2C-In1-C1 O2-In1-C1 O2A-In1-C1 C1B-In1-C1 C1C-In1-C1 C1A-In1-C1 C1-O1-In1 C1-O2-In1 C3-C2-C3D C3-C2-C1 C3D-C2-C1 O2-C1-O1 O2-C1-C2 O1-C1-C2 O2-C1-In1 O1-C1-In1 C2-C1-In1 C2-C3-C2E

2.409(5) 1.253(8) 1.245(8) 1.383(9) 1.390(10) 1.501(9) 1.390(10) 87.82(19) 80.5(2) 28.16(18) 103.61(18) 144.1(2) 97.1(3) 87.82(19) 122.6(2) 112.4(2) 28.19(18) 144.1(2) 103.61(18) 80.5(2) 28.16(18) 116.01(16) 116.00(16) 122.6(2) 87.82(19) 28.19(18) 112.4(2) 103.61(18) 144.1(2) 28.16(18) 80.5(2) 116.01(16) 116.00(16) 97.1(3) 97.5(4) 85.9(4) 120.8(7) 119.7(6) 119.5(6) 120.3(6) 120.9(6) 118.7(6) 66.0(4) 54.3(3) 172.6(5) 119.2(7)

a Symmetry transformations used to generate equivalent atoms: (A) 1 - x, 0.5 - y, z; (B) 0.25 + y, 0.75 - x, 0.25 - z;. (C) 0.75 - y, -0.25 + x, 0.25 - z; (D) -z + 1/2, -x + 1, y - 1/2; (E) -y + 1, z + 1/2, -x + 1/2.

nine indium ions encapsulate a large space. Nine indium ions can be evenly divided into three groups in terms of their positions. The first (In1, In1E, In1H) and the third groups (In1D, In1F, In1G) are coordinated by the basal btc groups, whereas

Figure 1. Coordination environment of In(III) atom in 1.

Figure 2. (left) View of an In9(btc)11 unit showing C3 axis. (right) Another view of an In9(btc)11cage. Symmetry code: (A) 0.5 + x, 0.5 + y, -0.5 + z; (B) 0.75 + z, 0.25 - y, 0.75 - x; (C) 0.75 - x, 0.25 - z, -0.75 + y; (D) 0.75 - z, 0.25 - y, -0.75 + x; (E) 1.25 - x, 0.75 - z, -0.25 + y; (F) 0.5 + x, 0.5 - y, -z; (G) 1.25 - x, 0.25 + z, -0.25 - y; (H) 0.25 + z, 0.75 - y, 0.25 - x; (I) 1 - x, 0.5 - y, z; (J) 0.25 + y, 0.75 - x, 0.25 - z.

the second group (In1A, In1B, In1C) bonds to lateral btc groups. The three groups of indium ions define three parallel equilateral triangles. The gigantic pore in the cage can be reflected by the following data: 20.1 Å, the edge length of triangle In1AIn1B-In1C in the middle of cage, and 8.8 Å, the distance between the top and the bottom basal btc groups. A 3-fold rotational axis passes through the centroids of the basal btc benzene rings and thus gives a C3 molecular symmetry. The cages aggregate together to give a 3D architecture with four channels running along the body diagonal directions of the cubic lattice. These four independent sets of channels having the same shape and size intersect at the abovementioned void spaces embraced by In9(btc)11 cages, resulting in a highly porous open framework (Figure 3). A better insight into the nature of this complicated framework can be achieved by the application of topological approach. As discussed above, the In atoms act as four-coordinate centers and btc ligands act as four-coordinate node. According to Wells,17 the framework can be represented topologically as (8,3/4)-a net. The long Schla¨fli symbol is 83‚ 83‚83‚83‚84‚84 for the In node and 85‚85‚85 for the btc ligand node, giving the net the symbol (85‚85‚85)4(83‚83‚83‚83‚84‚84)3, which can be represented by the short symbol (83)4(86)3 (see the Supporting Information, Figure S1). As estimated by the program PLATON,18 the extra framework volume within the crystal is calculated to be 65.4%, which is 5527 Å3 per unit cell. To the best of our knowledge, such non-interpenetrated anionic framework including benzenemulticarboxylate with high

1714 Crystal Growth & Design, Vol. 7, No. 9, 2007

Lin et al.

Figure 5. Luminescence excitation and emission spectra of complex 1 in the crystal state at RT.

Figure 3. (top) View of a channel (represented by the cyan hollow cylinders) and the voids (represented by the balls) encapsulated by In9(btc)11 units. (bottom) Conceptual presentation of the porous network of 1. The cyan hollow cylinders represent channels. The purple sticks correspond to the counterparts in Figure 2. Note that the balls connected by purple and yellow sticks designate indium ions.

Figure 4. Thermogravimetric curve of complex 1.

symmetry and large cages is seldom found. The examples we have known include the sodalite topology with the carbonate ion as a building block, [Cu6(CO3)12{C(NH2)3}8],4-7a a framework with mixed triangular and octahedral building blocks having the pyrite topology, [Zn4O(TCA)2]‚(DMF)3(H2O)3(TCA)4,4′,4′′-tricarboxy triphenylamine),7b a pair of interwoven metal-organic frameworks, Cu3(BTB)2(H2O)3(DMF)9(H2O)2(H3BTB ) 4,4′,4′′-benzene-1,3,5-triyl-tribenzoic acid),7d a framework having the NbO structure type Cu2[o-Br- C6H3(CO2)2]2(H2O)2‚(DMF)8(H2O)2,7e and a chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n (TMA ) btc).7f Our framework represents the first example of M6L8 anionic framework with open channels and cubic symmetry of this sort. Thermogravimetric analysis (TGA) was carried out in a flow of nitrogen atmosphere for complex 1. As shown in Figure 4, complex 1 loses most of the crystal water molecules (15.16%) at 141 °C and then continues to lose the rest of them (total 19.40%) at 340 °C. TGA data indicate that framework decomposition occurs between 380 and 560°. The remaining weight 21.36% is in agreement with the expected value 22.49% if the final residue is in the In2O3 phase. Complex 1 is also fluorescent in the solid state at room temperature (Figure 5) and can be excited with a wavelength of 474 nm, producing intense green luminescence with a peak maximum occuring at 535 nm. Because the H3btc emits luminescence in the range 370-380 nm with the excitation peak at 334 nm19 and tmdp do not emit

Figure 6. XRD patterns: (a) calculated on the basis of the [In6(btc)8]6unit, (b) as-synthesized sample, and (c-e) the inorganic ion-exchanged samples.

any luminescence in the range 400-800 nm, the emission of 1 may be attributed to the ligand-to-metal charge transfer (LMCT). Although some of d10 metal compounds with aromatic carboxylate ligands emit similar green or greenish blue fluorescences,20 the photophysical properties in indium(III)-organic coordination polymers are rarely reported in literature. Ion Exchange. In the typical ion-exchange experiments, original samples of 1 (about 40 mg) were immersed in a solution of KCl (18.2mmol, in 10 mL H2O), BaCl2 (4.1mmol, in 10 mL H2O), and NH4Cl (14.78mmol, in 30 mL H2O), respectively, and heated at 60 °C for 1 day. The products were then filtered out, washed with distilled water, and dried in air. The exchanged products became less crystalline after the experiments. Element microanalysis (For the K+-exchanged sample: C, 30.88; N, 1.19; H, 3.83; In, 22.80; K, 4.10. For the Ba2+-exchanged sample: C, 28.90; N, 0.87; H, 3.41; In, 20.80; Ba, 9.29. For the NH4+exchanged sample: C, 29.83; N, 2.60; H, 4.15) indicates that H2tmdp cations in 1 can be partially exchanged with the above inorganic ions. reflected by the decrease in C, N, and H contents. They were also characterized by X-ray powder diffractions (XRD), and the major XRD reflections of complex 1 and exchanged products are shown in Figure 6, confirming that their frameworks remain unchanged after ion exchanges.

Symmetric Porous Framework with Intersecting Open Channels

The other experiments were carried out in less-concentrated solutions of KCl (4.29mmol in 25 mL H2O, 32h), CaCl2 (1.88mmol in 25 mL H2O, 32h), Sr(NO3)2 (1.89mmol in 25 mL H2O, 32h), and BaCl2 (1.80mmol in 25 mL H2O), respectively. Their C, N, H contents were less varied. (For the K+-exchanged sample: C, 32.85; N, 1.76; H, 4.56. For the Ca2+exchanged sample: C, 32.57; N, 1.61; H, 4.49. For the Sr2+exchanged sample: C, 30.92; N, 1.46; H, 4.21. For the Ba2+exchanged sample: C, 32.47; N, 1.85; H, 4.37.) XRD and TGA were also used to characterize the phase changes of complex 1 for studying its stability of the structure. To remove a portion of the lattice water, we heated the crystalline powder of 1 at 140 °C for 2 h, which formed a partially dehydrated intermediate state. After that, the sample was exposed to a wet vapor atmosphere at room temperature for 24-48 h to generate the rehydrated phase of 1. The major XRD reflections of them, shown in Figure S2 in the Supporting Information, indicate that the framework of complex 1 remains unchanged after the hydrated phase is regenerated from its initial dehydrated phase. Acknowledgment. We acknowledge the support from the 973 Program (2006CB932900), the National Natural Foundation of China, and the Natural Science Foundation of Fujian Province. Supporting Information Available: X-ray crystallographic files in CIF format and XRD patterns for dehydrated and rehydrated phases of complex 1 (PDF). This material is available free of charge via the Internet at http://pubs.acs.org.

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