Four Cd-Based Metal–Organic Frameworks with Structural Varieties

May 22, 2013 - Abstract Image. Four three-dimensional (3D) Cd-based metal–organic frameworks (MOFs), [Cd(pyip)(dmf)] (1), [Cd(pyip)(doa)] (2), [Cd(p...
1 downloads 10 Views 3MB Size
Download PDF
Article pubs.acs.org/crystal

Four Cd-Based Metal−Organic Frameworks with Structural Varieties Derived from the Replacement of Organic Linkers Fang Wang,† Xuemin Jing,‡ Bing Zheng,† Guanghua Li,† Guang Zeng,† Qisheng Huo,† and Yunling Liu*,† †

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China ‡ Faculty of Chemistry and Material Science, Langfang Teachers College, Langfang 065000, P. R. China S Supporting Information *

ABSTRACT: Four three-dimensional (3D) Cd-based metal− organic frameworks (MOFs), [Cd(pyip)(dmf)] (1), [Cd(pyip)(doa)] (2), [Cd(pyip)(pz)] (3) and [Cd(pyip)(bipy)(H2O)0.5] (4) (dmf = N,N′-dimethylformamide, doa = 1,4-dioxane, pz = pyrazine, bipy = 4,4′-bipyridine) have been rationally designed and systematically synthesized by using 5-(pyridine-4-yl)isophthalic acid (H2pyip) and Cd(NO3)2·4H2O under solvothermal conditions. Compound 1 possesses a mineral-like 3,6connected rtl network, and compounds 2−4 exhibit a 3,5connected interpenetrating hms network constructed with 2-fold layers and bridging coligands pillars (doa, pz, and bipy), respectively. In compounds 2−4, doa, pz, and bipy act as pillars to extend the distance between the two layers from 7.34 to 11.36 Å, and the different conformations and lengths of the coligands have influenced the angles between the bridging ligands and the layers. Additionally, the four compounds exhibit strong luminescent emissions in the solid state at room temperature, and the latter three compounds exhibit robust architectures as evidenced by their permanent porosity and high thermal stability.

■

INTRODUCTION

Inspired by these ideas, we report here four MOFs, namely, [Cd(pyip)(dmf)] (1), [Cd(pyip)(doa)] (2), [Cd(pyip)(pz)] (3), and [Cd(pyip)(bipy)(H2O)0.5] (4), assembled from the reaction of Cd(NO3)2·4H2O and H2pyip by replacing half of the pyip structural organic linkers with coligands (doa, pz, bipy). As we expected, in compound 1, pip acted as a template to direct a 3,6-connected rtl network, and in compounds 2−4, doa, pz, and bipy served as pillars to support two layers, while forming pillar-layer, 3D interpenetrating structures with a 3,5connected hms network. In addition, thermogravimetric analysis revealed that compounds 2−4 possess robust architectures with high thermal stabilities, and luminescent properties of compounds 1−4 have also been investigated.

In recent years, a new class of microporous material known as metal−organic frameworks (MOFs) or porous coordination polymers (PCPs) has attracted great attention not only for their intriguing structural topologies but also for their potential applications as functional materials in the areas of gas adsorption, separation, catalysis, drug delivery, molecular magnetism, and photoluminescent properties.1,2 MOFs possess extended structures constructed with metal atoms or metaloxide clusters (secondary building units (SBUs)) and organic linkers.3 In principle, the rational design of organic ligands or coligands is one of the strategies for the assembly of structural controllable MOFs.4 Among the strategies, “pillar-layer” assembly and template-assisted syntheses have become two rational and effective ways to synthesize novel structures, and a great deal of significant work has been done by using the above two strategies.5,6 Among these organic ligands, pyridyl carboxylates have been a topic type of organic linker for they contain mixed N-,O-donors.7 Therefore, our group chose 5(pyridine-4-yl)isophthalic acid (H2pyip) as an organic ligand8 to use pillar-layer and template-assisted methods to design and synthesize MOFs. Then four different functional organic coligands, pip, doa, pz, bipy (pip = piperazine, doa = 1, 4dioxane, pz = pyrazine, bipy = 4,4′-bipyridine) were selected to be templates or pillars in our reaction system, which may have different impacts on the synthesis process. © XXXX American Chemical Society

■

EXPERIMENTAL SECTION

Material and Physical Measurements. All starting materials were purchased commercially and used without purification. Elemental analyses (C, H, and N) were performed on a Perkin-Elmer 2400 analyzer. Inductively coupled plasma (ICP) analyses were carried out on a Perkin-Elmer Optima 3300Dv spectrometer. IR spectra were recorded in the range of 400−4000 cm−1 on a Nicolet Impact 410 FTIR spectrometer using KBr pellets. Thermal gravimetric analysis (TGA) was performed on a TGA Q500 thermogravimetric analyzer in air condition with heating rates of 10 °C min−1. X-ray powder Received: April 3, 2013 Revised: May 21, 2013

A

dx.doi.org/10.1021/cg400486q | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Table 1. Crystal Data and Structure Refinement for Compounds 1−4 compound

1

2

3

4

formula fw temp (K) wavelength (Å) cryst syst space group a (Å) b (Å) c (Å) V (Å3) Z, Dc (Mg/m3) F(000) θ range (deg) reflns collected/unique Rint data/restraints/params GOF on F2 R1, wR2 (I > 2σ(I)) R1, wR2 (all data)

C16H14CdN2O5 426.69 293(2) 0.71073 monoclinic P21/c 9.2420(18) 18.201(4) 9.7270(19) 1579.7(5) 4, 1.794 848 3.12−27.44 19268/4126 0.0196 3587/30/217 1.045 0.0315, 0.0849 0.0348, 0.0862

C17H15CdNO6 441.70 293(2) 0.71073 monoclinic C2/c 10.170(2) 20.659(4) 7.6720(15) 1562.2(5) 4,1.878 880 3.16−27.42 32084/2807 0.0272 1766/0/116 1.156 0.0223, 0.0587 0.0235, 0.0592

C17H11CdN3O4 433.69 293(2) 0.71073 orthorhombic Cmcm 10.226(2) 20.706(4) 7.5525(15) 1599.1(5) 4, 1.785 856 3.34−25.00 8738/5835 0.0843 808/1/93 1.067 0.0447, 0.0968 0.0590, 0.1011

C23H16CdN3O4.5 518.79 293(2) 0.71073 monoclinic C2/m 20.827(4) 10.148(2) 11.790(2) 2397.1(8) 4, 1.413 1036 3.05−24.99 12038/2800 0.0577 2230/48/209 1.144 0.0569, 0.1579 0.0637, 0.1615

diffraction (XRD) data were collected on a Rigaku 2550 diffractometer with Cu Kα radiation (λ = 1.5418 Å) and a scan rate of 1.2°/min. Luminescent spectra were collected on a Fluoromax-4 spectrophotometer for the solid powder samples at room temperature. Synthesis of Compound 1. A solid mixture of H2pyip (0.005 g, 0.02 mmol), pip (0.002 g, 0.023 mmol), Cd(NO3)2·4H2O (0.0035 g, 0.011 mmol), dmf (0.5 mL), EtOH (0.25 mL), and HNO3 (0.4 mL, 4.3 M in dmf) were sealed in a 20 mL vial and then heated at 85 °C for 24 h. Light yellow block crystals were collected and washed with dmf and then dried in air (59% yield based on H2pyip). ICP and elemental analysis (wt %) for 1: calcd Cd 21.7, C 45.0, H 3.31, N 6.7; found Cd 20.1, C 47.2, H 3.51, N, 6.9. IR (KBr pellet, cm−1) 3300 m, 3071 w, 1655 s, 1609 s, 1570 s, 1499 w, 1447 m, 1290 m, 1218 m, 930 m, 840 m, 774 s, 729 s, 644 s, 572 w, 507 m, 429 w. Synthesis of Compound 2. A solid mixture of H2pyip (0.005 g, 0.02 mmol), Cd(NO3)2·4H2O (0.0035 g, 0.011 mmol), dmf (0.5 mL), doa (0.25 mL), H2O (0.25 mL), and HNO3 (0.4 mL, 4.3 M in dmf) were sealed in a 20 mL vial and heated at 85 °C for 24 h. Light yellow block crystals were collected and washed with dmf and then dried in air (56% yield based on H2pyip). ICP and elemental analysis (wt %) for 2: calcd Cd 25.5, C 46.2, H 3.42, N 3.2; found Cd 24.5, C 48.1, H 3.6, N 3.5. IR (KBr pellet, cm−1) 3465 w, 3079 m, 1722 m, 1611 s, 1559 s, 1500 m, 1448 m, 1370 s, 1291 m, 1239 m, 1024 m, 1017 m, 854 s, 776 s, 730 s, 645 s, 567 w, 495 m, 450 m. Synthesis of Compound 3. A solid mixture of H2pyip (0.005 g, 0.02 mmol), Cd(NO3)2·4H2O (0.0035 g, 0.011 mmol), pz (0.002 g, 0.025 mmol), dmf (0.5 mL), H2O (0.25 mL), and HNO3 (0.1 mL, 4.3 M in dmf) were sealed in a 20 mL vial and heated at 85 °C for 24 h. Colorless block crystals were collected and washed with dmf and then dried in air (54% yield based on H2pyip). ICP and elemental analysis (wt %) for 3: calcd Cd 25.9, C 47.1, H 2.51, N 9.7; found Cd 24.9, C 46.2, H 2.71, N 9.3. IR (KBr pellet, cm−1) 3430 m, 3078 w, 1714 w, 1616 s, 1557 s, 1505 m, 1459 m, 1374 s, 1290 m, 918 m, 839 m, 728 s, 730 s, 644 s, 572 w, 500 m, 441 s. Synthesis of Compound 4. A solid mixture of H2pyip (0.0050 g, 0.02 mmol), Cd(NO3)2·4H2O (0.0035 g, 0.011 mmol), bipy (0.004 g, 0.025 mmol), dmf (0.5 mL), H2O (0.25 mL), and HNO3 (0.1 mL, 4.3 M in dmf) were sealed in a 20 mL vial and heated at 85 °C for 24 h. Light yellow block crystals were collected and washed with dmf and then dried in air (yield 43% based on H2pyip). ICP and elemental analysis (wt %) for 4: calcd Cd 21.7, C 53.3, H 3.11, N 8.1; found Cd 20.9, C 51.2, H 3.22, N 8.1. IR (KBr pellet, cm−1) 3430 m, 3058 m, 1675 m, 1609 s, 1557 s, 1505 m, 1446 m, 1368 s, 1296 m, 878 m, 839 m, 774 s, 728 s, 644 m, 572 w, 500 m, 454 w.

The phase purity of as-synthesized samples was confirmed by the evident similarities between the simulated and experimental X-ray powder diffraction patterns (as seen in Supporting Information, Figure S1). The as-synthesized 1−4 were insoluble in water and common organic solvents, and the framework still remained stable, which was confirmed by the XRD of solvent-exchanged samples (see Supporting Information, Figure S2). The IR spectra for 1−4 were shown in Supporting Information, Figure S4. X-ray Structure Determinations. Suitable single crystals of 1−4 were selected for single-crystal X-ray diffraction analyses. Crystal data for 1−4 were collected on a Rigaku RAXIS-RAPID diffractometer using Mo Kα radiation (λ = 0.71073 Å). The structures were solved by direct methods and refined by full-matrix least-squares on F2 using SHELXTL Version 5.1.9 All the metal atoms were located first, and then the oxygen and carbon atoms of the compounds were subsequently found in difference Fourier maps. The hydrogen atoms of the ligands were placed geometrically, and the hydrogen atoms of the water molecules could not be located but were included in the formula. All non-hydrogen atoms were refined anisotropically. The final formula was derived from crystallographic data combined with elemental and thermogravimetric analysis data. Crystallographic data for 1−4 (CCDC 913326−913329) have been deposited with Cambridge Crystallographic Data Centre. Data can be obtained free of charge upon request at www.ccdc.cam.ac.uk/data_request/cif. The detailed crystallographic data and structure refinement parameters for 1−4 are summarized in Table 1. Topology information was obtained using TOPOS 4.0 program.10

■

RESULTS AND DISCUSSION Crystal Structure of 1. Crystal structure determination reveals that 1 crystallizes in monoclinic space group P21/c. The asymmetric unit of 1 contains two equivalent Cd(II) atoms; each Cd(II) atom is in a five-coordinated mode, CdO4N, in which each cadmium metal is bonded to three carboxyl oxygen atoms, one carboxyl O atom is from the pyip2− in a monodentate manner, the other two adjacent bridging carboxyl O atoms in a bidentate manner are from different pyip2− ligands, and the remaining one O atom is from the dmf molecule, and one N atom from the pyip2− ligand (Figure 1a). The Cd−O bond lengths vary from 2.297(2) to 2.526(3) Å, and the Cd−N bond length is 2.291(3) Å, which are in the normal ranges in both cases. Each pyip2− unit coordinates to three metal centers as a 3-connected node (Figure 1b). B

dx.doi.org/10.1021/cg400486q | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 1. (a) The coordination environment of binuclear Cd(II) viewed as a 6-connected node; (b) the ligand H2pyip coordinates three binuclear cadmium units and viewed as a 3-connected node; (c) The 3D framework of 1; (d) 3D topology with 3,6-connected rtl net; (e) 1D channel along [010]; (f) the left- and right-handed helices in the 1D channel; (g) double-stranded meso-helix in 1D channel; (h) each 1D channel with a left-handed and a right-handed helix. Color code: Cd, green; O, red; C, gray; N, blue. (Hydrogen atoms and guest molecules have been omitted for clarity.)

Figure 2. (a) Cd(II) center with three H2pyip ligands and two linkers doa, pz, bipy and viewed as 5-connected node. (b) The ligand H2pyip with three Cd(II) center and viewed as a 3-connected node; (c) 2D grid motif based on Cd(II) and 3-connected ligand; (d) 3D framework by using doa, pz, and bipy stacking in a staggered fashion; (e) polyhedron view of the hms net. (Hydrogen atoms have been omitted. Cd: green; C: gray; N: blue; O: red.)

Considering the narrow bite angles of the bidentate carboxylate ions, the geometry of the binuclear Cd(II) is probably best described as a distorted octahedron. The pyip2− ligands act as bridging linkers, and the N atoms coordinate with binuclear centers to construct a three-dimensional (3D) framework (Figure 1c) with left- and right-handed helical chains. Hence, the binuclear Cd(II) center, which is connected with six pyip2− ligands and two dmf molecules, can be simplified to be a 6connected node. The ligand pyip2− coordinates with three binuclear Cd(II) centers that can be seen as a 3-connected node. Consequently, the structure of 1 can be described as a 3,6-connected network (Figure 1d), which belongs to minerallike rtl network with Schläfli symbols {4.62} and {42.610.83}. As shown in Figure 1e, the pyip2− ligand bridges the Cd(II) to form a one-dimensional (1D) infinite chain of [Cd3pyip4]∞ around the crystallographic 21 axis with a pitch of 11.540 Å. It is interesting to note that the 1D chain contains two types of helices: a left- and right-handed sequence (Figure 1f) to generate a double-stranded meso-helix (Figure 1g). Each 1D chain, comprised of double-stranded helices (Figure 1h), coordinates with the adjacent chain through bridging O atoms from pyip2− to form a mesomeric 3D framework. The total solvent-accessible volume for 1 is 32.3%. The pore diameter of channel in 1 is 8.2 × 8.2 Å2 (Figure S5). The results of PXRD and TGA analysis indicate that the terminal DMF molecular in 1 cannot be exchanged by other solvents (Figures S2 and S3), and N2 adsorption experiments did not exhibit microporosity. Crystal Structure of 2−4. X-ray single-crystal structure analysis reveals that 2 crystallizes in the monoclinic space group C2/c and is a 3D, interpenetrating framework constructed by 2fold layers and pillars. The Cd(II) center is seven-coordinated, CdO6N, with four carboxyl O atoms from two different pyip2− ligands in a bidentate mode, the remaining two O atoms are from polar doa molecules, and one N atom is from the other pyip2− ligand (Figure 2a). The Cd−O bond distances are in the

range of 2.251(18)−2.554(2) Å, and the Cd−N bond distance is 2.276(3) Å, which are in the normal ranges as reported in related species. Each pyip2− unit is completely deprotonated and coordinates to three metal centers acting as a 3-connected node (Figure 2b) to form a 2D layer with honeycomb pores (Figure 2c). The adjacent layers are connected through the doa molecules with the Cd(II) centers and give rise to the overall 3D pillar-layer structure, with an approximate distance of 7.7 Å between adjacent layers, which results in much a more spacious structure that allows a second framework to interpenetrate the first (Figure 2d). Consequently, the Cd(II) center can be regarded as a 5-connected node in a trigonal bipyramid geometry, incorporating with the 3-connected ligand in a triangle geometry to result in a 3,5-connected hms network (Figures 2e and 3b). To the best of our knowledge, networks

Figure 3. (a) Topological features of 1 displayed by tiling style; (b) topological features of 2−4 displayed by tiling style. C

dx.doi.org/10.1021/cg400486q | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

containing 5-connected nodes are rarely reported.11 Compounds 3 and 4 have the same coordination mode as compound 2: Cd(II) and H2pyip ligands connect to construct a 2D-sheet with honeycomb pores (Figure 2c), and adjacent sheets are linked by pz and bipy ligands through their coordinated nitrogen atoms to form two 3D frameworks, respectively, as seen in Figure 2d. Then, the 3-connected ligand (Figure 2b) and 5-connected Cd(II) centers are further connected to form the 2-fold interpenetrating hms network (Figure 2e). In the non-interpenentrating network, compounds 2−4 all exhibit four different types of infinite channels. In 2, the pore diameters are 8.0 × 11.3 Å2, 7.3 × 11.3 Å2, 7.3 × 10.2 Å2, and 7.3 × 5.1 Å2. In 3, the pore diameters are 8.1 × 11.3 Å2, 7.6 × 11.3 Å2, 7.6 × 10.2 Å2, and 7.6 × 5.1 Å2. In 4, there are four different types of channels with diameters of 10.1 × 11.4 Å2, 9.3 × 11.4 Å2, 7.7 × 11.5 Å2, and 5.6 × 11.4 Å2 (point-to-point and not including van der Waals radii). While one framework interpenetrates the second to form a 2-fold interpenetrating network, the pore diameters in 2−4 almost decrease by half. The total solvent-accessible volume for 2−4 has been estimated, using PLATON.12 The unit cells of compounds 2 and 3 contain no residual solvent accessible void since the bridging linkers are not long enough when constructing the 2fold interpenetrating structure. The total solvent-accessible volume for 4 is 17.9%. Structure analysis of 2−4 indicated that when H2pyip was allowed to coordinate with Cd(II) in dmf/H2O solvent, the [Cd(pyip)] 2D layered structure is preferred. Furthermore, the layered structure could be supported by using pillared ligands such as doa, pz, and bipy to construct layer-pillar 3D architectures. This synthetic strategy allows the systematic variation of the pillar ligands to generate open frameworks with tunable window dimensions and pore volumes from 7.34 to 11.36 Å. The structures of compounds 2−4 are all 2-fold interpenetrating frameworks, and this study shows that the colinker length is not only responsible for the degree of the interpenetration, but the bulkiness of the colinkers also affects the degree of the interpenetration in the pillar layered structures.13 In 2−4, the change in ligands from doa, pz, to bipy, however, results in considerable distortion of these nets. The doa ligand is in chair conformation and leads the angle between the doa bridging ligands and the sheets to be approximately 76° (Figure S6a). The pz coligands and the sheets are at an angle of nearly 90° (Figure S6b), while the angle between bipy bridging ligands and the sheets are approximately 75° (Figure S6c), bringing the sheets close together and increasing the packing efficiency of the networks. In 4, there is space occupied by solvent H2O molecules between layers. The narrow part of the bipy bridge where one pyridine moiety joins the other also allows the coligand of the steric maneuverability to pass through the second framework’s sheets at varying angles, a feature not possessed by the doa or pz bridges. Another interesting feature of these three related structures is the decrease in symmetry from orthorhombic (pz) to monoclinic (doa, bipy) as the framework becomes more distorted. Thermogravimetric Analysis. The thermal stability of compounds 1−4 hs been evaluated in the temperature range of 30−800 °C under air atmosphere (Figure S7). Compound 1 exhibits the first mass loss of 16.15% below 240 °C due to the release of dmf molecules (calcd 17.11%); the further weight loss of 55.32% between 240 and 470 °C can be

attributed to decomposition of the organic ligands (calcd 56.5%), and the postresidue is CdO (JCPDS: 65-2908), which has been confirmed by XRD analysis. The TG curve of 2 exhibits a major weight loss of 72.31% in the temperature range of 250−470 °C due to the release of pyip2− ligands and doa molecules (calcd 74.55%). The final product is CdO (JCPDS: 65-2908), which has been confirmed by XRD analysis. Compound 3 exhibits a major weight loss of 72.03% in the temperature range of 110−500 °C, corresponding to the release of the pyip2− ligands and pz molecules (calcd 73.62%); the final product is CdO, which was confirmed by XRD analysis. The TG curve of compound 4 shows the first mass loss of 1.99% below 360 °C due to the release of H2O molecules (calcd 1.73%); the further weight loss of 71.23% between 360 and 454 °C should be attributed to the decomposition of the organic H2pyip and bipy ligands (calcd 76.59%); the final product is CdO (JCPDS: 65−2908), which was verified by XRD analysis. To confirm the robustness of the framework, compounds 1− 4 were calcinated from 35 to 450 °C, respectively. The corresponding XRD patterns reveal that 1 remains stable when heated to 200 °C (Figure S8), and 2−3 can retain their frameworks after being heated to 400 °C. In compound 4, the corresponding XRD patterns are different from as-synthesized 4, which is due to the release of guest H2O molecules (Figure S9). Luminescent Properties. Luminescent properties of compounds containing d10 metal centers have attracted intense interest due to their potential applications, such as in chemical sensors, photochemistry, electroluminescent displays, and so on.14 In this work, the photoluminescent spectra of H2pyip and compounds 1−4 have been carried out at room temperature in the solid state. The main emission peaks of H2pyip is at 430 nm, which can be attributed to π* → n or π* → π transitions.15 As shown in Figure 4, compound 1 exhibits an intensive blue

Figure 4. Luminescent spectra of solid ligand H2pyip and 1−4.

luminescence emission at 465 nm, while compounds 2−4 display green luminescence emissions at 433, 440, and 437 nm, respectively, which is red-shifted in comparison to the H2pyip ligand. The Cd(II) ions are difficult to oxidize or reduce because of the d10 configuration. As a result, the emissions of the four compounds are neither metal-to-ligand charge transfer (MLCT) nor ligand-to-metal charge transfer (LMCT).16 The emission peak of compound 1 is highly red-shifted relative to the free H2pyip, which probably can be assigned as arising from D

dx.doi.org/10.1021/cg400486q | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Stoddart, J. F.; Yaghi, O. M. Science 2012, 336, 1018. (j) Zou, C.; Wu, C.-D. Dalton Trans. 2012, 3879. (k) Perry, Iv, J. J.; Feng, P. L.; Meek, S. T.; Leong, K.; Doty, F. P.; Allendorf, M. D. J. Mater. Chem. 2012, 22, 10235. (l) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem. Soc. Rev. 2009, 38, 1330. (m) Dhakshinamoorthy, A.; Garcia, H. Chem. Soc. Rev. 2012, 41, 5262. (3) (a) Li, Y.-A.; Ren, S.-K.; Liu, Q.-K.; Ma, J.-P.; Chen, X.; Zhu, H.; Dong, Y.-B. Inorg. Chem. 2012, 51, 9629. (b) Zheng, S.-T.; Wu, T.; Chou, C.; Fuhr, A.; Feng, P.; Bu, X. J. Am. Chem. Soc. 2012, 134, 4517. (c) Zhong, D.-C.; Deng, J.-H.; Luo, X.-Z.; Liu, H.-J.; Zhong, J.-L.; Wang, K.-J.; Lu, T.-B. Cryst. Growth Des. 2012, 12, 1992. (d) Vilhelmsen, L. B.; Walton, K. S.; Sholl, D. S. J. Am. Chem. Soc. 2012, 134, 12807. (e) Bon, V.; Senkovskyy, V.; Senkovska, I.; Kaskel, S. Chem. Commun. 2012, 48, 8407. (f) Park, I.-H.; Kim, K.; Lee, S. S.; Vittal, J. J. Cryst. Growth Des. 2012, 12, 3397. (g) Wang, X.-S.; Chrzanowski, M.; Kim, C.; Gao, W.-Y.; Wojtas, L.; Chen, Y.-S.; Peter Zhang, X.; Ma, S. Chem. Commun. 2012, 48, 7173. (h) Senchyk, G. A.; Bukhan’ko, V. O.; Lysenko, A. B.; Krautscheid, H.; Rusanov, E. B.; Chernega, A. N.; Karbowiak, M.; Domasevitch, K. V. Inorg. Chem. 2012, 51, 8025. (i) Song, S.-Y.; Song, X.-Z.; Zhao, S.-N.; Qin, C.; Su, S.-Q.; Zhu, M.; Hao, Z.-M.; Zhang, H.-J. Dalton Trans. 2012, 41, 10412. (4) (a) Xue, M.; Zhu, G.; Ding, H.; Wu, L.; Zhao, X.; Jin, Z.; Qiu, S. Cryst. Growth Des. 2009, 9, 1481. (b) Ferrando-Soria, J.; Serra-Crespo, P.; de Lange, M.; Gascon, J.; Kapteijn, F.; Julve, M.; Cano, J.; Lloret, F.; Pasán, J.; Ruiz-Pérez, C.; Journaux, Y.; Pardo, E. J. Am. Chem. Soc. 2012, 134, 15301. (c) Martinez Casado, F. J.; Canadillas-Delgado, L.; Cucinotta, F.; Guerrero-Martinez, A.; Ramos Riesco, M.; Marchese, L.; Rodriguez Cheda, J. A. CrystEngComm 2012, 14, 2660. (d) Habib, H. A.; Hoffmann, A.; Hoppe, H. A.; Janiak, C. Dalton Trans. 2009, 10, 1742. (e) Cui, G.-H.; He, C.-H.; Jiao, C.-H.; Geng, J.-C.; Blatov, V. A. CrystEngComm 2012, 14, 4210. (5) (a) Eubank, J. F.; Wojtas, L.; Hight, M. R.; Bousquet, T.; Kravtsov, V. Ch.; Eddaoudi, M. J. Am. Chem. Soc. 2011, 133, 17532. (b) Li, Z.-X.; Zhao, J.-P.; Sañudo, E. C.; Ma, H.; Pan, Z.-D.; Zeng, Y.F.; Bu, X.-H. Inorg. Chem. 2009, 48, 11601.. (c) Chang, Z.; Zhang, D.S.; Chen, Q.; Li, R.-F.; Hu, T.-L.; Bu, X.-H. Inorg. Chem. 2011, 50, 7555. (d) Tan, Y.-X.; He, Y.-P.; Zhang, J. Inorg. Chem. 2012, 51, 9649. (e) Henke, S.; Schneemann, A.; Wütscher, A.; Fischer, R. A. J. Am. Chem. Soc. 2012, 134, 9464. (f) Otsubo, K.; Haraguchi, T.; Sakata, O.; Fujiwara, A.; Kitagawa, H. J. Am. Chem. Soc. 2012, 134, 9605. (g) Song, P.; Liu, B.; Li, Y.; Yang, J.; Wang, Z.; Li, X. CrystEngComm 2012, 14, 2296. (6) (a) Jing, X.; Zhang, L.; Ma, T.; Li, G.; Yu, Y.; Huo, Q.; Eddaoudi, M.; Liu, Y. Cryst. Growth Des. 2009, 10, 492. (b) Chen, S.-C.; Zhang, Z.-H.; Zhou, Y.-S.; Zhou, W.-Y.; Li, Y.-Z.; He, M.-Y.; Chen, Q.; Du, M. Cryst. Growth Des. 2011, 11, 4190. (c) Bernini, M. a. C.; Snejko, N.; Gutierrez-Puebla, E.; Brusau, E. V.; Narda, G. E.; Monge, M. A. n. Inorg. Chem. 2011, 50, 5958. (d) Ma, L.; Lin, W. J. Am. Chem. Soc. 2008, 130, 13834. (e) Yuan, R.; Chen, C.; Zhang, N. J. Inorg. Organomet. Polym. 2012, 22, 507. (f) Panda, T.; Pachfule, P.; Banerjee, R. Chem. Commun. 2011, 47, 7674. (g) Yang, G.-S.; Zang, H.-Y.; Lan, Y.-Q.; Wang, X.-L.; Jiang, C.-J.; Su, Z.-M.; Zhu, L.-D. CrystEngComm 2011, 13, 1461. (h) Sha, J.-Q.; Sun, J.-W.; Wang, C.; Li, G.-M.; Yan, P.-F.; Li, M.-T.; Liu, M.-Y. CrystEngComm 2012, 14, 5053. (7) (a) Jing, X.; Meng, H.; Li, G.; Yu, Y.; Huo, Q.; Eddaoudi, M.; Liu, Y. Cryst. Growth Des. 2010, 10, 3489. (b) Qin, L.; Hu, J.-S.; Huang, L.F.; Li, Y.-Z.; Guo, Z.-J.; Zheng, H.-G. Cryst. Growth Des. 2010, 10, 4176. (c) Liu, X.; Oh, M.; Lah, M. S. Cryst. Growth Des. 2011, 11, 5064. (d) Zhao, B.; Yi, L.; Dai, Y.; Chen, X.-Y.; Cheng, P.; Liao, D.-Z.; Yan, S.-P.; Jiang, Z.-H. Inorg. Chem. 2005, 44, 911. (e) Sharma, M. K.; Senkovska, I.; Kaskel, S.; Bharadwaj, P. K. Inorg. Chem. 2010, 50, 539. (f) Wang, P.; Moorefield, C. N.; Panzer, M.; Newkome, G. R. Chem. Commun. 2005, 35, 4405. (8) (a) Li, H.; Shi, W.; Zhao, K.; Niu, Z.; Chen, X.; Cheng, P. Chem. − Eur. J. 2012, 18, 5715. (b) Liu, Y.; Li, H.; Han, Y.; Lv, X.; Hou, H.; Fan, Y. Cryst. Growth Des. 2012, 12, 3505. (c) Xiang, S.; Huang, J.; Li, L.; Zhang, J.; Jiang, L.; Kuang, X.; Su, C.-Y. Inorg. Chem. 2011, 50, 1743. (d) Thomas, J. A. Dalton Trans. 2011, 40, 12005.

the strong interaction between the ligand and metal, while the slight red-shift for compounds 2−4 can be due to the H2pyip ligand and the bridging linker connected to the metal center.17

■

CONCLUSIONS In conclusion, we have successfully constructed four novel MOFs by adding four coligands (pip, doa, pz, and bipy), in which pip is used as template while doa, pz, bipy are used as bridging linkers to construct a series of pillar-layers with similar open frameworks, and the coligand effects have been evaluated. The different conformations and lengths among the coligands have impacted the angle between the bridging ligands and the layers. Compound 1 is a 3D framework with rtl network topology, and compounds 2−4 are 2-fold interpenetrating structures with a rare 3,5-connected hms network. The luminescent properties of compounds 1−4 indicate that they may be good candidates for luminescent materials with robust frameworks and thermal stability.

■

ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format, powder XRD patterns, IR spectra, and TG curves, as well as some structure views of the compounds. This information is available free of charge via the Internet at http://pubs.acs.org/.

■

AUTHOR INFORMATION

Corresponding Author

*Fax: +86-431-85168624. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We gratefully acknowledge the financial support of the Natural Science Foundation of China (Grant Nos. 21071059 and 21171064) and the Program for New Century Excellent Talents in University (NCET-10-0439).

■

REFERENCES

(1) (a) Davies, R. P.; Less, R.; Lickiss, P. D.; Robertson, K.; White, A. J. P. Cryst. Growth Des. 2010, 10, 4571. (b) Gu, Z.-G.; Liu, Y.-T.; Hong, X.-J.; Zhan, Q.-G.; Zheng, Z.-P.; Zheng, S.-R.; Li, W.-S.; Hu, S.J.; Cai, Y.-P. Cryst. Growth Des. 2012, 12, 2178. (c) He, K.-H.; Li, Y.W.; Chen, Y.-Q.; Song, W.-C.; Bu, X.-H. Cryst. Growth Des. 2012, 12, 2730. (d) Gedrich, K.; Senkovska, I.; Baburin, I. A.; Mueller, U.; Trapp, O.; Kaskel, S. Inorg. Chem. 2010, 49, 4440. (2) (a) Niu, D.; Yang, J.; Guo, J.; Kan, W.-Q.; Song, S.-Y.; Du, P.; Ma, J.-F. Cryst. Growth Des. 2012, 12, 2397. (b) Cai, Y.; Zhang, Y.; Huang, Y.; Marder, S. R.; Walton, K. S. Cryst. Growth Des. 2012, 12, 3709. (c) Zhao, J.; Wang, X.-L.; Shi, X.; Yang, Q.-H.; Li, C. Inorg. Chem. 2011, 50, 3198. (d) Lincke, J.; Lässig, D.; Kobalz, M.; Bergmann, J.; Handke, M.; Möllmer, J.; Lange, M.; Roth, C.; Möller, A.; Staudt, R.; Krautscheid, H. Inorg. Chem. 2012, 51, 7579. (e) Wang, C.; deKrafft, K. E.; Lin, W. J. Am. Chem. Soc. 2012, 134, 7211. (f) Das, M. C.; Guo, Q.; He, Y.; Kim, J.; Zhao, C.-G.; Hong, K.; Xiang, S.; Zhang, Z.; Thomas, K. M.; Krishna, R.; Chen, B. J. Am. Chem. Soc. 2012, 134, 8703. (g) Wee, L. H.; Wiktor, C.; Turner, S.; Vanderlinden, W.; Janssens, N.; Bajpe, S. R.; Houthoofd, K.; Van Tendeloo, G.; De Feyter, S.; Kirschhock, C. E. A.; Martens, J. A. J. Am. Chem. Soc. 2012, 134, 10911. (h) Colombo, V.; Montoro, C.; Maspero, A.; Palmisano, G.; Masciocchi, N.; Galli, S.; Barea, E.; Navarro, J. A. R. J. Am. Chem. Soc. 2012, 134, 12830. (i) Deng, H.; Grunder, S.; Cordova, K. E.; Valente, C.; Furukawa, H.; Hmadeh, M.; Gándara, F.; Whalley, A. C.; Liu, Z.; Asahina, S.; Kazumori, H.; O’Keeffe, M.; Terasaki, O.; E

dx.doi.org/10.1021/cg400486q | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

(9) Sheldrick, G. M. SHELXTL-97, Program for Crystal Structure Refinement; University of Göttingen: Göttingen, Germany. (10) Blatov, V.; Shevchenko, A.; Serezhkin, V.; Korchagin, D.http:// www.topos.ssu.samara.ru. (11) (a) Abrahams, B. F.; Batten, S. R.; Hoskins, B. F.; Robson, R. Inorg. Chem. 2003, 42, 2654. (b) Huang, Z.; Song, H.-B.; Du, M.; Chen, S.-T.; Bu, X.-H.; Ribas, J. Inorg. Chem. 2003, 43, 931. (c) Kong, D.; Zoñ, J.; McBee, J.; Clearfield, A. Inorg. Chem. 2006, 45, 977. (d) Sun, D.; Luo, G.-G.; Zhang, N.; Wei, Z.-H.; Yang, C.-F.; Huang, R.-B.; Zheng, L.-S. Chem. Lett. 2010, 39, 190. (e) Zhu, H.-L.; Sun, Z.Y.; Rong, N.-N.; Zhang, B.; Zhang, M.; Li, Y. Acta Crystallogr. E. 2003, 59, m906. (f) Behera, J. N.; Rao, C. N. Can. J. Chem. 2005, 83, 668. (g) Masciocchi, N.; Attilio Ardizzoia, G.; Brenna, S.; Castelli, F.; Galli, S.; Maspero, A.; Sironi, A. Chem. Commun. 2003, 16, 2018. (h) Pan, L.; Finkel, B. S.; Huang, X.; Li, J. Chem. Commun. 2001, 1, 105. (i) Dong, Y.-B.; Ma, J.-P.; Huang, R.-Q.; Liang, F.-Z.; Smith, M. D. Dalton Trans. 2003, 8, 1472. (j) Ding, B.; Yi, L.; Wang, Y.; Cheng, P.; Liao, D.-Z.; Yan, S.-P.; Jiang, Z.-H.; Song, H.-B.; Wang, H.-G. Dalton Trans. 2006, 5, 665. (k) Gao, C.; Liu, S.; Xie, L.; Ren, Y.; Cao, J.; Sun, C. CrystEngComm 2007, 9, 545. (12) Spec, A. L. J. Appl. Crystallogr. 2003, 36, 7. (13) Farha, O. K.; Malliakas, C. D.; Kanatzidis, M. G.; Hupp, J. T. J. Am. Chem. Soc. 2009, 132, 950. (14) (a) Wu, Q.; Esteghamatian, M.; Hu, N.-X.; Popovic, Z.; Enright, G.; Tao, Y.; D’Iorio, M.; Wang, S. Chem. Mater. 2000, 12, 79. (b) McGarrah, J. E.; Kim, Y.-J.; Hissler, M.; Eisenberg, R. Inorg. Chem. 2001, 40, 4510. (c) Santis, G. D.; Fabbrizzi, L.; Licchelli, M.; Poggi, A.; Taglietti, A. Angew. Chem., Int. Ed. 1996, 35, 202. (15) (a) Shi, X.; Zhu, G.; Fang, Q.; Wu, G.; Tian, G.; Wang, R.; Zhang, D.; Xue, M.; Qiu, S. Eur. J. Inorg. Chem. 2004, 1, 185. (b) Zhang, X. M.; Tong, M. L.; Gong, M. L.; Chen, X. M. Eur. J. Inorg. Chem. 2003, 1, 138. (c) Tian, G.; Zhu, G. S.; Fang, Q. R.; Guo, X. D.; Xue, M.; Sun, J. Y.; Qiu, S. L. J. Mol. Struct. 2006, 787, 45. (d) Wen, L.; Li, Y.; Lu, Z.; Lin, J.; Duan, C.; Meng, Q. Cryst. Growth Des. 2006, 6, 530. (e) Wen, L.; Lu, Z.; Lin, J.; Tian, Z.; Zhu, H.; Meng, Q. Cryst. Growth Des. 2007, 7, 93. (f) Lin, J.-G.; Zang, S.-Q.; Tian, Z.-F.; Li, Y.Z.; Xu, Y.-Y.; Zhu, H.-Z.; Meng, Q.-J. CrystEngComm 2007, 9, 915. (16) (a) Yang, Y.; Du, P.; Ma, J.-F.; Kan, W.-Q.; Liu, B.; Yang, J. Cryst. Growth Des. 2011, 11, 5540. (b) Niu, D.; Yang, J.; Guo, J.; Kan, W.-Q.; Song, S.-Y.; Du, P.; Ma, J.-F. Cryst. Growth Des. 2012, 12, 2397. (c) Lu, W.-G.; Deng, J.-H.; Zhong, D.-C. Inorg. Chem. Commun. 2012, 20, 312. (d) Liao, S.-Y.; Gu, W.; Yang, L.-Y.; Li, T.-H.; Zhang, M.; Wang, L.; Liu, X. Polyhedron 2012, 36, 38. (e) Kan, W.-Q.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. Polyhedron 2011, 30, 2106. (17) (a) Wen, G.-L.; Wang, Y.-Y.; Zhang, W.-H.; Ren, C.; Liu, R.-T.; Shi, Q.-Z. CrystEngComm 2010, 12, 1238. (b) Zhang, W. H.; Dong, Z.; Wang, Y. Y.; Hou, L.; Jin, J. C.; Huang, W. H.; Shi, Q. Z. Dalton Trans. 2011, 40, 2509.

F

dx.doi.org/10.1021/cg400486q | Cryst. Growth Des. XXXX, XXX, XXX−XXX