Assembly of a Three-Dimensional Metal–Organic Framework with

Article pubs.acs.org/crystal

Assembly of a Three-Dimensional Metal−Organic Framework with Copper(I) Iodide and 4‑(Pyrimidin-5-yl) Benzoic Acid: Controlled Uptake and Release of Iodine Jing Wang,† Jiahuan Luo,† Xiaolong Luo,† Jun Zhao,‡ Dong-Sheng Li,*,‡ Guanghua Li,† Qisheng Huo,† and Yunling Liu*,† †

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China ‡ College of Mechanical & Material Engineering, Research Institute of Materials, China Three Gorges University, Yichang 443002, China S Supporting Information *

ABSTRACT: A novel three-dimensional metal−organic framework, [Cu2I2]0.5[Cu2(CO2)4(C10H7N2)4]0.5·2DMF (JLU-Liu14), has been synthesized under solvothermal conditions, which is constructed by ternary secondary building units (SBUs): classical Cu2(CO2)4 paddle-wheel unit, Cu2I2 dimer unit, and organic SBU. In JLU-Liu14, the pyrimidine groups of 4PmBC (4-(pyrimidin-5-yl) benzoic acid) ligands coordinated to copper paddle-wheel and Cu2I2 dimer units to form a zigzag chain, and the zigzag chains then connected together by 4-PmBC ligands to generate a threedimensional framework with (3,4,6)-connected topology. There are two types of channels along the c axis with the dimensions of 14 × 14 Å and 5 × 5 Å, respectively, in which the big hexagonal channel is surrounded by six small trigonal channels. In addition, JLU-Liu14 displays the interesting ability of the uptake and release of iodine.

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(3D) MOFs structures based on CunIn clusters.39−41 For instance, Zhang and co-workers reported a zeolite MTN-type cluster-organic framework by tetrahedral Cu4I4 clusters and linear dabco ligands, which exhibited perfect integration of porosity and photoluminescent properties from both the cluster and the framework in a porous material.42 Therefore, CunIn clusters are good building units for the construction of novel and functional frameworks. To the best of our knowledge, iodine is one of the necessary rare elements for the human body. The importance of iodine can be attributed to the treating iodine deficiency and hypothyroidism, disinfecting germs, promoting absorption of vitamins, enhancing enzyme activity, and so on. On the other hand, the enhancement of radioactive iodine in the waste of the nuclear industry is dangerous and can destroy the health of humans, which is very difficult to deal with. Recently, several groups have chosen effective methods by using MOFs materials to dispose of iodine.43−50 For example, Zeng’s group reported a highly stable MOF with rigid metal−organic pillars, which exhibited kinetics of iodine loading and release in comparison to zeolite 13X and activated carbon.51 Volkringer’ group reported a series of aluminum-based MOFs for sorption of

INTRODUCTION Recently, assembly and functionalization of zeolites and metal− organic frameworks (MOFs) materials have captivated much attention not only because of their intriguing structures,1−6 but also due to their ground potential applications in gas storage,7−10 carbon dioxide capture,11−14 separation,15,16 catalysis,17,18 drug delivery,19,20 magnetism,21−23 and sensing,24−26 etc. The design and preparation of crystalline materials with novel topologies and desired functions are very important topics and also great challenges in this field.27,28 Up to now, thousands of MOFs with interesting structures and functional properties have been reported depending on organic ligands, metal ions/metal clusters, reaction conditions, temperature, pH value, and so on.29−31 In order to build different dimensional frameworks, the crucial step is to choose metal ions/metal clusters as nodes and multifunctional organic ligands as linkers. CuI has the stronger capability to form the diverse clusters due to the variety of coordination geometries for Cu(I) and the potential bridging capability for I− anion, such as Cu2I2 rhomboid dimers,32−34 Cu4I4 cubane tetramers,35,36 and Cu6I6 hexagonal prisms.37,38 Thus, rational design and construction of MOFs with the CunIn clusters as the nodes has become the current subject. So far, some intriguing MOFs have been successfully synthesized by the reaction of CuI and organic ligands, including a series of one-dimensional (1D) chain, two-dimensional (2D) layer, and three-dimensional © XXXX American Chemical Society

Received: November 27, 2014 Revised: December 30, 2014

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Crystal Growth & Design iodine in cyclohexane.52 Among the various adsorbent materials, MOFs appear to be one of the most effective candidates for the capture of iodine. As a continuation of our previous work,53 here we used the ternary secondary building units (SBUs) approach to construct MOF material with one kind of organic SBU and two kinds of inorganic SBUs. We choose the less reported 4-(pyrimidin-5yl) benzoic acid (4-PmBC)54,55 ligand with multidentate Nand O-donors as organic linkers to react with copper(I) iodide, in which Cu+ ions can be easily converted into Cu2+ ions with the changes of the external environment.56,57 Additionally, the N-donors easily coordinate with Cu+ and I− ions to form CunIn cluster, while the O-donors easily coordinate with Cu2+ ions to result in the formation of Cu2(CO2)4 paddle-wheel unit. As expected, a novel MOF based on a ternary SBUs including classical Cu2(CO2)4 paddle-wheel unit, Cu2I2 dimer unit, and organic SBU has been successfully constructed, namely, [Cu 2 I 2 ] 0.5 Cu 2 (CO 2 ) 4 (C 10 H 7 N 2 ) 4 ] 0.5 ·2DMF (JLU-Liu14), which displays a new (3,4,6)-connected topology with two different shapes of channels of the dimensions of 14 × 14 Å and 5 × 5 Å, respectively. More interestingly, the iodine molecules can move freely in and out of the framework.

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Table 1. Crystal Data and Structure Refinement for JLULiu14

EXPERIMENTAL SECTION a

Physical Measurements and Materials. The ligand was synthesized according to the literature procedure.58 All the other chemical reagents were obtained from commercial sources, which were used without further purification. Powder X-ray diffraction (PXRD) data were collected on a Rigaku D/max-2550 diffractometer with Cu Kα radiation (λ = 1.5418 Å). C, H, and N elemental analyses were achieved by using vario MICRO elementar. The infrared (IR) spectra of compounds were recorded on a Nicolet Impact 410 FTIR spectrometer with KBr pellets in the range of 400−4000 cm−1. The thermal gravimetric analyses (TGA) were collected on TGA Q500 thermogravimetric analyzer used in air (heating rate of 10 °C min−1). UV/vis spectra were recorded on an UV-2450 UV−visible spectrophotometer within 200−600 nm by using the same solvent as the blank. Synthesis of JLU-Liu14. A mixture of CuI (0.005 g, 0.03 mmol), 4PmBC (0.005 g, 0.03 mmol), and N,N-dimethylformamide (DMF) (1 mL) were added into a 20 mL vial, respectively. The mixture was sonicated for 5 min. And the vial was sealed and heated at 85 °C for about 24 h, after which green polyhedral crystals were abtained and dried in air (67% yield based on CuI). C, H, N elemental analysis (wt %) for JLU-Liu14: calcd C 42.11, H 3.53, N 10.52; found C 42.01, H 3.38, N 10.35. FT-IR (KBr, cm−1): 3426 (m), 3058 (w), 2920 (w), 1609 (s), 1401 (s), 1186 (m), 1006 (m), 784 (s), 708 (s), 492 (w). X-ray Crystallography. Crystallographic data for JLU-Liu14 were collected on a Bruker Apex II CCD diffractometer using Mo-Kα (λ = 0.71073 Å) radiation at room temperature. The structure was obtained by direct method and refined by full-matrix least-squares on F2 using SHELXTL Version 5.1.59 Metal atoms were located first, and then the carbon, oxygen, and nitrogen atoms of the compound were subsequently found in difference Fourier maps. The hydrogen atoms of the ligand were placed geometrically. All non-hydrogen atoms were refined anisotropically. Since the highly disordered guest DMF molecules were trapped in the channels of JLU-Liu14 and partial guest DMF molecules could not be modeled properly by SHELXTL, the final formulas were derived from crystallographic data combined with thermogravimetric analysis data and elemental data. Crystallographic data for JLU-Liu14 (1033732) has been deposited with Cambridge Crystallographic Data Centre. These data can be obtained free of charge upon request by www.ccdc.cam.ac.uk/data_request/cif. Crystal data as well as detailed data collection and refinement for JLULiu14 are summarized in Table 1. Topology information for JLULiu14 was calculated by TOPOS 4.0.60,61

compound

JLU-Liu14

formula fw temp (K) crystal syst space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dc (Mg/m3) μ (mm−1) F(000) reflections collected reflections unique Rint GOF on F2 R1, wR2 [I > 2σ(I)]a R1, wR2 (all data)a

C28H28Cu2IN6O6 798.55 296(2) trigonal R3̅ 40.979(4) 40.979(4) 16.064(3) 90 90 120 23362(5) 18 0.952 1.439 6606 26142/12575 [R(int) = 0.0537] 0.974 0.0643, 0.1602 0.1321, 0.1951

R1 = ∑||Fo| − |Fc||/∑|Fo|. wR2 = [∑[w(F02 − Fc2)2]/∑[w(F02)2]]1/2.

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RESULTS AND DISCUSSION Crystal Structure of JLU-Liu14. JLU-Liu14 crystallizes in the trigonal space group of R3̅. The asymmetric unit of JLULiu14 is made up of two independent copper atoms, two ligand molecules, and one iodine ion. The copper atoms exhibit two different coordination modes; Cu1 atom is 1+ and displays tetrahedral [CuN2I2] geometry with two N atoms from two individual 4-PmBC ligands and two iodine ions (Figure S3a, Supporting Information). Two Cu(I) atoms are coordinated together by two iodine anions to afford a bimetallic Cu2I2 dimer unit with the Cu(I)···Cu(I) distance about 2.601 Å, which can be simplified into a 4-connected node (Figure 1). The Cu2 atom is 2+ and displays square pyramidal [CuNO4] geometry with one N atom and four O atoms from five distinct 4-PmBC ligands (Figure S3b, Supporting Information). Two Cu (II) atoms are bridged by four carboxylate groups in a bridging bidentate fashion to give a classical Cu2(CO2)4 paddle-wheel unit with the Cu (II)···Cu (II) distance about 2.631 Å, in which the axial positions are occupied by two pyrimidinyl N-donors from another two different 4-PmBC ligands, and the copper paddle-wheel unit can be simplified into a 6-connected node (Figure 1). The Cu1−N bond distance is in the range of 2.063−2.072 Å. The Cu1−I bond distance is in the range of 2.6193−2.6514 Å. The Cu2−O and Cu2−N bond distances are in the range of 1.954−1.973 and 2.687 Å, respectively. The different oxidation states of Cu ions are confirmed by X-ray photoelectron spectroscopy (XPS) (Figure S4, Supporting Information). In the structure of JLU-Liu14, the 4-PmBC ligand adopts two types of coordination modes, possessing similar dihedral angles between two aromatic rings and different distorted angles between the aromatic rings and carboxyl (Figure S5, Supporting Information), which can be simplified into a 3-connected and 2-connected nodes, respectively (Figure 1). Thus, the 3D framework of JLU-Liu14 can be described as a novel (3,4,6)-connected net referring to the RCSR database (Figure S6a, Supporting Information), which exhibit two B

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Crystal Growth & Design

of the solvent area volume of 15746 Å3, which represents 67% per unit cell volume (Figure 3c).

Figure 1. Ligand, Cu2I2 dimer unit, and Cu2(CO2)4 paddle-wheel unit can be viewed as 2,3,4,6-connected nodes.

distinct tiles: [56.92] and [518.92] (Figure S7, Supporting Information). In JLU-Liu14, the copper paddle-wheel units and Cu2I2 dimer units are linked by the pyrimidine groups of the 4-PmBC ligands to form a zigzag chain (Figure 2a), and the adjacent

Figure 3. (a) A big hexagonal channel; (b) a small trigonal channel; (c) the accessible surface of JLU-Liu14 (ignore the guest molecules).

4-PmBC ligand has rarely been explored to construct MOFs, which exhibits two types of coordination modes in the reported MOFs as seen in Scheme 1a,b, including one 0D cluster in (a) coordination mode,54 and one 3D framework in the (b) coordination mode by our group.55 The multidentate 4-PmBC ligand with hybrid N−O donors can coordinate with metal ions in a variety ways to give rise to a series of novel MOFs with interesting topologies and properties. More coordination modes of 4-PmBC ligand should be adequately discovered by the reasonable selection of metal ions. Here, we used mixed Cu2I2 dimer unit and Cu2(CO2)4 as inorganic building units to react with 4-PmBC ligand, and two novel coordination modes (c) and (d) have been explored. In (c) mode, the ligand as a 3connector coordinated with two Cu2+ metal ions in bis-O,Obridging mode and one Cu+ ions in N-monodentate mode; in (d) mode, the ligand as a 4-connector coordinated with three Cu2+ metal ions in bis-O,O-bridging and N-monodentate modes and one Cu+ ions in N-monodentate mode. As expected, some new coordination modes (Scheme 1e−l) may be found in the future.

Figure 2. (a) A zigzag chain; (b) the adjacent zigzag chains further connect via ligands to generate a 3D framework.

zigzag chains further connect via 4-PmBC ligands to generate a 3D network (Figure 2b). There are two types of channels along the c axis with the dimensions of 14 × 14 Å and 5 × 5 Å, respectively, in which the big hexagonal channel is surrounded by six small trigonal channels (Figure 3a,b). PLATON62 analysis shows that the 3D structure of JLU-Liu14 is composed C

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Crystal Growth & Design Scheme 1. Several Coordination Modes of the 4-PmBC Ligands a−la

Figure 4. (a) Photographs displayed the color change when a single crystal of JLU-Liu14a was immersed in the ethanol solution of I2 with time; (b) I2 adsorption progress of JLU-Liu14a when 50 mg of crystals was soaked in 3 mL of ethanol solution of I2; (c) I2 release progress of JLU-Liu14a immersed in 3 mL of ethanol solution.

40 h (Figure 4b), while the color of crystals of JLU-Liu14a was observed to go from green to black (Figure S9, Supporting Information), after which crystals of JLU-Liu14b were obtained and included a maximum of 0.5 I2 being adsorbed per formula unit. In fact, when JLU-Liu14a was immersed in another solution of I2, such as cyclohexane, benzene, and methanol, the color of the crystals experienced similar behaviors. Fourthly, the evolution of UV/vis spectrum for the release of iodine in the ethanol solution showed λmax at 204, 288, and 360 nm (Figures 5 and S10). The intensity of absorption bands became stronger

a

Color scheme: carbon, gray; nitrogen, blue; oxygen, red; metal, green; different metals or valence state, pink.

Thermogravimetric Analysis (TGA). As shown in Figure S8 (Supporting Information), the TGA curve for JLU-Liu14 indicates the weight loss of 16% within 30−250 °C, which belongs to the loss of guest DMF molecules. The weight loss of 64% within 250−560 °C occurs due to the collapse of the 3D framework (calcd: 65%). PXRD reveals that over 560 °C, the final sample is the pure dense copper oxide (JCPDS: 65-2309). Iodine Adsorption Properties. To explore the adsorption and release of iodine in JLU-Liu14, we performed distinct tests. First, the crystals of JLU-Liu14 were solvent exchanged with dry ethanol for 2 days, and the ethanol replaced the DMF in the pores of crystals, after which the desolvated crystals of JLULiu14a were obtained. Second, we selected a single crystal to immerge in the ethanol solution of I2 (0.01 M), which showed the size and shape of crystal has not changed during the adsorption process but the color has increased from green to black with time (Figure 4a). Third, we soaked 50 mg of single crystals of JLU-Liu14a in 3 mL of dry ethanol solution of I2 in a small sealed glass vial at room temperature, and we found that the dark brown solutions of I2 fade slowly to light brown after

Figure 5. UV/vis absorption spectra for the release of the I2 into ethanol solution.

with the increase of I2 molecules. The intensity of absorption band at 204 nm should be due to the concentration of I2, and the absorption bands at 288 and 360 nm should be ascribed to the polyiodide I3−, which was generally stabilized by H+ ions and gotten from the reaction of iodide with decomposed iodide.51 The delivery of I2 in ethanol increased linearly with time, and the release rate of JLU-Liu14b was estimated to be about 0.5 × 10−6 mol·L−1·min−1 based on the calibration plot of standard iodine (Figure S11, Supporting Information). Eventually, the color of crystals was observed from black to green. The X-ray powder diffraction patterns proved that the framework of JLU-Liu14 retained the host framework D

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ACKNOWLEDGMENTS The authors gratefully acknowledge the financial support of the Natural Science Foundation of China (Grant Nos. 21373095, 21373122, and 21171064).

crystallinity after uptake and release of the iodine (Figure S12, Supporting Information). Here, we report a new MOF constructed by the ternary SBUs including classical Cu2(CO2)4 paddle-wheel unit, Cu2I2 dimer unit, and organic SBU. The strategy of ternary SBUs utilized by us here is rarely reported. Up to now, in some copper(I) iodide structures, the organic components acting as linkers are usually multidentate N-donor ligands including imidazole, triazole, tetrazole, benzotriazole, and 1,4diazabicyclo[2.2.2]octane (dabco).63−65 To the best of our knowledge, few examples of 3D MOFs with a classical Cu2(CO2)4 paddle-wheel unit and a Cu2I2 dimer unit have been reported. The framework of JLU-Liu14 displays a novel (3,4,6)-connected net. The topologies of (3,4,6)-connected net include agw, asc, idp, epy, gao, hmc, mmn, ood, pdp, twf-d, and so on referring to the RCSR database, which exhibit different point symbols and tiles.1,66−68 Three-connected SBU is consisted of trigonal shape, 4-connected SBU is comprised of square and tetrahedral shape, and 6-connected SBU consists of octahedral and triangular prism shape. In the structure of JLULiu14, the copper paddle-wheel unit and Cu2I2 dimer unit can be simplified into an octahedral 6-connected node and a square 4-connected node, and the 4-PmBC linker can be considered as a trigonal 3-connected node. Additionally, JLU-Liu14 displays the ability of the uptake and release of iodine at room temperature, which includes a maximum of 0.5 I2 being adsorbed per formula unit. In comparison, the uptake of I2 being adsorbed per formula unit is lower than MOF {[Zn3(DLlac)2(pybz)2]·3I2}n reported by Zeng’s group,51 and similar to MOF {[Cu(btz)]·0.5I2}n.48 The different maximum amount of I2 being adsorbed per formula unit may be attributed to the different pore sizes and the strong interaction between the host and I2 molecules.

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CONCLUSIONS In summary, we successfully constructed a novel MOF based on a ternary SBUs including 4-PmBC ligand, Cu2(CO2)4 paddle-wheel unit, and Cu2I2 dimer unit by self-assembly under solvothermal conditions. JLU-Liu14 exhibits big hexagonal and small trigonal channels along the c axis. The 3D framework of JLU-Liu14 can be described as a (3,4,6)connected topology. Furthermore, we explored the uptake and release ability of iodine in JLU-Liu14, and it indicated that iodine inclusion in the crystals of JLU-Liu14 can be slowly released to the ethanol solution. More research around the adsorption and release of iodine is ongoing in our group. ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format, table for selected bonds and distances for JLU-Liu14, IR spectra, thermogravimetric analysis, topology information, and tiling for JLU-Liu14. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*(Y.L.) Fax: +86-431-85168624. E-mail: [email protected]. *(D.-S.L.) E-mail: [email protected]. Notes

The authors declare no competing financial interest. E

DOI: 10.1021/cg501730q Cryst. Growth Des. XXXX, XXX, XXX−XXX

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DOI: 10.1021/cg501730q Cryst. Growth Des. XXXX, XXX, XXX−XXX