CdII Terephthalate with Bis

(b) Mitzi , D. B.; Wang , S.; Field , C. A.; Chess , C. A.; Guloy , A. M. Science 1995, 267, 1473– 1476. [Crossref], [PubMed], [CAS]. 5. Conducting ...
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Coordination Assembly of ZnII/CdII Terephthalate with BisPyridinecarboxamide Tectons: Establishing Net Entanglements from [3 + 3] Interpenetration to High-Connected Self-Penetration Zhi-Hui Zhang,† Sheng-Chun Chen,† Ming-Yang He,† Qun Chen,*,† and Miao Du*,‡ †

Key Laboratory of Fine Petrochemical Technology, Changzhou University, Changzhou 213164, P. R. China College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Tianjin Normal University, Tianjin 300387, P. R. China

‡

S Supporting Information *

ABSTRACT: Four polymeric d10 metal terephthalate complexes incorporating bis-pyridinecarboxamide building blocks were prepared to explore the effect of the central metal ion or the fluorine substituent of the ligand on the topology and entanglement of coordination networks. The combination of ZnII terephthalate with a fluorinated ligand leads to a noninterpenetrated coordination layer with honeycomb (hcb) topology for complex 1. Interestingly, the other three materials display the unusual entangling coordination networks. For 2, the reaction of zinc terephthalate with nonfluorinated ligand affords three-dimensional diamond (dia) architecture of [3 + 3] interpenetration, while the CdII terephthalate complexes 3 and 4 with the two types of bis-pyridinecarboxamide tectons show the isostructural self-penetrating framework with unique 8-connected (417.611) topology.

comparison with their analogues, the fluorinated dipyridyl ligands have been seldom applied to design and construct coordination polymers.12 Recently, we have initiated the assembly of novel coordination systems by the judicious use of a fluorinated dipyridyl amide ligand, N,N′-[(2,3,5,6tetrafluoro-1,4-phenylene)bis(methylene)]bis(pyridine-4-carboxamide)13 (H2tfpbbp, Scheme 1). Our previous work shows

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rystal engineering and supramolecular chemistry of coordination polymers or metal−organic frameworks1 (MOFs) is attracting great attention for their intriguing supramolecular topologies and potential properties such as adsorption,2 ion exchange,3 magnetism,4 conductivity,5 chirality,6 catalysis,7 and nonlinear optics,8 etc. With respect to coordination networks, entanglement motifs are of special interest, which have been reviewed by Batten, Robson, and Ciani et al.9 In this context, the conformational versatility of flexible ligands will increase the difficulty in the construction of desired coordination frameworks with predesigned structures but promote the possibility in the formation of unusual supramolecular architectures such as entangling motifs. For example, the flexible ligand 1,3-bis(4-pyridyl)propane10 can adopt different conformations including anti−anti, gauche−anti, and two types of gauche−gauche forms, which may thus result in diverse interesting frameworks with new topologies or entanglements. In consideration of the multiple and intricate factors that may have significant impacts on the crystalline networks, the prediction and design of entangling architectures still represents a great challenge at present. In this connection, the exploitation of flexible ligands for coordination assembly will be helpful to further enrich and develop the structural paradigms of net entanglements. At the same time, the halogen substitution in crystal engineering is of great interest to both MOFs and supramolecular networks for halogen atoms (especially fluorine) and may readily adjust the resulting coordination arrays, the host organizations, and the possible included cavities.11−14 In © XXXX American Chemical Society

Scheme 1

that H2tfpbbp is a promising flexible bidentate ligand with bifunctional binding sites for coordination and H-bonding interactions and is confirmed to direct the extended networks showing conformational isomerism and varied entanglements. In the case of two layered CuII coordination polymers,13b the flexible ligand is responsible for the significant discrepancy of two open and close two-dimensional (2D) networks, while the Received: January 9, 2013 Revised: February 17, 2013

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introduction of aromatic dicarboxylates into the assembled systems can regulate the polymeric entangling coordination frameworks from 2D to three-dimensional (3D).13c In addition, the abundant fluorinated aromatic groups therein may influence the fluorescence intensity of the resulting complexes.14 In the present study, this fluorinated dipyridyl amide ligand is further applied as the organic linker with terephthalic acid (H2tp) as the coligand, aiming to construct novel coordination polymers with attractive entangling frameworks and fluorescence properties. To clearly evaluate the effect of fluorinated groups of ligand on coordination assembly, the corresponding nonfluorinated dipyridyl amide ligand, N,N′-[(1,4-phenylene) bis(methylene)]bis(pyridine-4-carboxamide) (H2pbbp, see Scheme 1), has also been explored. As a result, four different coordination frameworks of d10 metal terephthalates and H2tfpbbp or H2pbbp linkers will be presented herein. The reaction of ZnII or CdII acetate, H2tfpbbp or H2pbbp, and H2tp in a water solution under hydrothermal conditions results in four coordination polymers, 1 5 namely {[Zn2(H2tfpbbp)(tp)2(H2O)2]·2H2O}n (1), [Zn(H2pbbp)(tp)]n (2), {[Cd(H2tfpbbp)(tp)(H2O)]·H2O}n (3), and {[[Cd(H2pbbp)(tp)(H2O)]·H2O}n (4). Notably, these complexes can be prepared reliably in the temperature range from 120 to 180 °C, with the crystalline samples obtained in different qualities. All products were characterized by IR and elemental analysis, and their phase purities were confirmed by powder Xray diffraction (PXRD) patterns (see Figure S4 of the Supporting Information). Furthermore, their crystal structures were determined by X-ray single crystal analysis (see Table S1 of the Supporting Information).16 With H2tfpbbp, zinc acetate, and H2tp as starting materials under hydrothermal conditions,15 complex 1 was obtained with the chemical formula of {[Zn2(H2tfpbbp)(tp)2(H2O)2]·2H2O}n, which exhibits a three-connected 2D 63 honeycomb network with hcb topology. The central Zn1 ion shows a tetrahedral coordination environment being bound to one pyridyl group of H2tfpbbp [Zn1−N1, 2.056(2) Å], one water molecule [Zn1−O6, 1.979(2) Å], and two monodentate carboxylate groups from two independent tp ligands [Zn1−O2, 1.926(2) Å; Zn1−O4, 1.915(2) Å] (see Figure S1 and Table S2 of the Supporting Information). Each H2tfpbbp ligand takes the trans conformation to avoid the steric hindrance, connecting the adjacent ZnII ions into a rather flat 2D honeycomb network with the auxiliary tp spacers (Figure 1a). A large 74-membered ring window is constituted by six ZnII ions, double H2tfpbbp, and four tp molecules, which can be idealized to an unequilateral hexagon in the chair conformation. In each hexagonal unit, the Zn···Zn edge lengths are 19.13, 10.97, and 10.98 Å, respectively, and the maximum Zn···Zn diagonal separation is 31.17 Å. These layers stack in a parallel fashion along the [010] axis with slightly interdigitation (Figure 1b). Interlayer voids are calculated17 to be 49.1 and 74.8 Å3, respectively, before and after, excluding the water guests therein, indicating the modest capability of guest capture. Notably, the bidentate pyridyl amide tecton, bearing the Hbonding sites of −NH groups, is interlinked to the uncoordinated carboxylate oxygen of tp via a N2−H2A···O5 interaction. At the same time, the other tp tecton also forms a hydrogen-bonding interaction (O6−H6B···O3) with the aqua ligand. Thus, each molecular building block, consisting of the metal ion, tp spacer, and bidentate H2tfpbbp, can be regarded as a 4-connected node due to the combination of both coordination and H-bonding interactions. As a result, the final

Figure 1. (a) A perspective view of the 2D coordination network of 1 with the ZnII centers represented as blue polyhedra. (b) Perspective (top) and side (bottom) views of the H-bonding interactions between the adjacent honeycomb (hcb) layers.

3D supramolecular structure is very complicated, which topologically shows a 3-nodal 4-connected network with the total point symbol of (4.6.84)2(42.82.92)(64.82)2. Additionally, the lattice water molecule also plays an essential role in stabilizing the overall 3D crystalline lattice via H-bonding interactions with the host coordination framework that is also reinforced by weak C−H···F interactions (see Table S4 of the Supporting Information for details). H2tfpbbp has a relatively flexible structure with little conformational control over the directionality of −NH hydrogen bonding donors. When this ligand is changed to its nonfluorinated analogue H2pbbp, the polymeric ZnII coordination framework of complex 2 displays a unique 3D entangling arrangement with [3 + 3] fold interpenetration of the dia nets. The asymmetric unit consists of two ZnII centers, two tp anions, and two H2pbbp ligands in gauche conformation (Figure 2a). The H2pbbp ligands connect the adjacent ZnII ions to form a one-dimensional [Zn(H2pbbp)] undulated singlestranded chain extending along the [100] direction, with the Zn···Zn separations of 20.034(1) and 19.551(1) Å, respectively. Further, the tp anions crosslink these chains to afford infinite strings running along the [001] direction, where the adjacent ZnII ions are bridged with the Zn···Zn distances of 10.696(2) and 10.941(2) Å, respectively. Both Zn1 and Zn2 adopt the distorted tetrahedral geometry provided by two pyridyl N atoms from H2pbbp and two carboxylate O atoms from tp. The considerable distortion is reflected by the large angles of 121.5(2)° for O3−Zn1−O5 and 117.1(2)° for O9−Zn2−N5. B

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Figure 2. Views of 2. (a) The asymmetric unit with coordination environments of ZnII centers. (b) A single dia net of the coordination array with one [Zn(H2pbbp)] chain highlighted in purple. (c) Perspective and schematic illustration of the [3 + 3] interpenetration.

Figure 3. Views of 3. (a) A local view with atom labeling. (b) 3D coordination framework (the penetrated tp linkers are indicated as purple rods). (c) A schematic illustration of the 8-connected self-penetrating architecture.

distance of 3.44 Å between the pyridyl group of one ligand and the xylene moiety of a second coligand. Hydrothermal reaction15 of Cd(OAc)2·2H2O, H2tfpbbp, and H2tp yields colorless crystals of 3. Crystallographic study16 reveals that 3 crystallizes in space group C2/c to show a 3D binodal (4,5)-connected coordination framework. In the asymmetric unit of 3, there are one CdII center, one tp anion, two halves H2tfpbbp ligands, one coordinated water, and one lattice water (Figure 3a). Each CdII ion is six-coordinated with an octahedral sphere, which is supplied by two carboxylate O, one amide O, and one water O to define the equatorial plane, as well as two pyridine N atoms that locate at the axial sites with the N1−Cd1−N3 angle of 167.6(1)° (Figure 3a). The Cd−O bonds distances are in the range of 2.320(1) to 2.446(1) Å and the Cd−N ones are 2.339(2) and 2.344(2) Å

The 3D architecture for a single net shows a dia topological prototype with the presence of large channels along the [001] axis (see Figure 2b), where the 4-connected ZnII nodes are extended by the bridging spacers. As indicated by structural analysis using TOPOS,18 the overall 3D array is a [3 + 3] interpenetrating network with the dia topology (see Figure 2c). Analysis of the crystal packing also reveals the presence of multiple N−H···OC interactions. As a result, an H-bonding dimer is formed via N7−H7AA···O1 and N6−H6A···O2, which is further connected to other dimers through N2−H2A···O7 and N3−H3A···O8 interactions (see Figure S2 of the Supporting Information). Thus, the entanglement coordination framework is extended to a 3D supramolecular architecture, allowing additional weak C−H···π interactions with the C

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Thermogravimetric analysis (TGA) experiments were conducted to study the thermal stability of complexes 1−4, which is an important parameter for the applications of coordination polymers. As shown in Figure S3 of the Supporting Information, the first weight loss occurring in the ranges of 70−125 °C for 1, 100−150 °C for 3, and 100−140 °C for 4, which corresponds to the release of lattice water. And the coordination frameworks of 1−4 remain intact upon further heating to 230, 260, 250, and 290 °C, respectively. For 1 and 2, decomposition of the coordination network represents two consecutive weight losses in the temperature ranges of 230− 460 °C and 260−490 °C, respectively. In spite of the isostructural nature of 3 and 4, the TGA curve of 4 suggests a stricter decomposition because of the metal−ligand synergistic effects. Coordination polymers involving d10 metal centers and aromatic organic ligands can be considered a new type of luminescent material.20 Thus, the photoluminescence properties of 1−4 and the two free ligands were investigated in the solid state at room temperature, with the emission spectra shown in Figure 4. Excitation of the samples at 333−337 nm

(see Table S3 of the Supporting Information). The anionic tp ligand takes the bis-monodentate coordination mode to bridge the adjacent CdII ions with a distance of 11.731(1) Å. Both crystallographic independent H2tfpbbp ligands adopt the anti conformations but with different binding fashions; that is, each centrosymmetric ligand connects four CdII ions using the pyridyl N and carbonyl O donors to serve as a tetradentate building block, whereas the C2-related ligand is bound to two CdII centers, in which the two terminal pyridyl groups are inclined to each other with the dihedral angle of 62.5(2)°. As a result, each CdII center can be considered as a 5connected square-pyramidal node, by linking to two 4connected H2tfpbbp ligands, one bridging H2tfpbbp, and two bridging tp spacers, to afford a 3D (4,5)-connected coordination network with an unprecedented (42.84)(43.6.86)2 topology. Notably, such a binodal (4,5)-connected net also represents the feature of self-penetration, as illustrated in Figure 3b. In this unique network, the nearest Cd···Cd separation is 8.206(2) Å with two CdII centers bridged by a pair of pyridyl and carbonyl, where two parallel pyridyl groups are involved in π−π interactions with the centroid-to-centroid distance of 3.588(2) Å. From another viewpoint of topology, if this binuclear subunit works as the network node, the resulting array is a uniform 8-connected self-penetrating network with an unprecedented (417.611) topology (Figure 3c). Notably, the most successful approach so far for the synthesis of selfpenetrating architecture is to build polynuclear metal clusters with the aid of dicarboxylate and/or exobidentate bridged ligands. The known 8-connected self-penetrating networks scope from the familiar ilc net (424.5.63), which can be viewed as two interpenetrating pcu nets cross-linked by two extra connections from each net node along the cube diagonals to (424.64), (420.68), and (416.612) topological nets, etc.19 Complex 3 undoubtedly shows a new 8-connected self-penetrating topology, which can be ascribed to the different conformations and coordination modes of the two kinds of H2tfpbbp ligands. In addition, the volume percent occupied by the lattice water molecule is 1.2% (64.7 Å3) of the unit cell, as calculated by PLATON.17 Analysis of the crystal packing also reveals the presence of N−H···O interactions, which are similar to those observed in complex 1. Unlike the couple of ZnII complexes, complex 4 is isostructural to 3, although the nonfluorinated ligand H2pbbp is used. They have similar structural features such as metalcoordination environments, network topologies, and Hbonding interactions, which indicates that the tetrafluorinated group of the ligand makes no impact on their coordination assemblies with CdII ions as metal centers. Recently, we have initiated the study of the coordination assemblies containing fluorinated dipyridyl-type ligand and ZnII ions, which exhibit unique entangled frameworks with both self-penetrating and interpenetrating structural features.13c In accordance with the previous investigation, ZnII ions show reliable tetrahedral geometry but the related coordination assemblies are significantly influenced by the subtle substituent groups on isophthalic acid (H2ip) coligands, which may be attributed to the small radii of ZnII centers. So, it can be expected that a slight change of the fluorinated dipyridyl-type ligands may lead to the structural regulation of ZnII polymers (1 and 2). While in the cases of CdII ions having larger radii, the contribution of the fluorinated groups does not change the coordination modes and has little influence on the structural assemblies of the CdII polymers (3 and 4).

Figure 4. Solid state emission spectra of complexes 1−4 and the free ligands.

leads to the generation of intense fluorescence emissions. Similar emission maxima (1, 489/518 nm; 2, 478/517 nm; 3 and 4, 478/518 nm) of 1−4 were observed in the blue region, which can be attributed to the n→π* electronic transitions of the ligand-centered aromatic systems. The considerable enhancement for these peaks, compared to those of free H2tfpbbp and H2pbbp ligands, may be attributed to the increased rigidity of the ligand when it is bound to a metal center, which effectively reduces the loss of energy.21 Notably, the free terephthalic acid ligand exhibits maximum emission intensity at about 390 nm in the solid state22, and this emission is far away from the emissions of complexes. So, the bispyridinecarboxamide ligands play a key role in the fluorescence properties of complexes, despite the fluorescence nature of the ligands themselves has no significant influence on the intensity of all complexes. Remarkably, the CdII complexes exhibit stronger emission peaks than those of ZnII complexes, and the intensity discrepancy for ZnII and CdII complexes likely arises from the incorporation of different metal−ligand coordination interactions. D

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In summary, four novel d10 metal terephthalate coordination polymers incorporating a pair of flexible pyridinecarboxamide ligands have been hydrothermally synthesized and structurally characterized. This work demonstrates that the flexible pyridinecarboxamide ligands are nice candidates to construct entangled coordination networks. The slight change of the fluorinated groups on these ligands plays a key role on the formation of distinct 2D and 3D coordination networks for ZnII complexes (1 and 2) but has little influence on the structural assemblies of the CdII systems (3 and 4). Significantly, the alteration of metal ions not only leads to an occurrence of the [3 + 3] interpenetration of the dia framework for 2, but also results in two isostructural 8-connected self-penetrating networks with dinuclear nodes in 3 and 4. The synergistic effect of metal centers and pyridinecarboxamide ligands will be responsible for the construction of these well-regulated coordination architectures with unusual network entanglements.

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2077. (g) Liu, D.; Lang, J.-P.; Abrahams, B. F. J. Am. Chem. Soc. 2011, 133, 11042−11045. (3) (a) Fang, Q.-R.; Zhu, G.-S.; Xue, M.; Sun, J.-Y.; Qiu, S.-L. Dalton Trans. 2006, 2399−2402. (b) Du, M.; Zhao, X.-J.; Guo, J.-H.; Batten, S. R. Chem. Commun.(Cambridge, U. K.) 2005, 4836−4838. (c) Zhang, X.-M.; Tong, M.-L.; Lee, H. K.; Chen, X.-M. J. Solid State Chem. 2001, 160, 118−122. (d) James, S. L. Chem. Soc. Rev. 2003, 32, 276−288. (4) (a) Barthelet, K.; Marrot, J.; Riou, D.; Férey, G. Angew. Chem., Int. Ed. 2002, 41, 281−284. (b) Cave, D.; Gascon, J. M.; Bond, A. D.; Teat, S. J.; Wood, P. T. Chem. Commun.(Cambridge, U. K.) 2002, 1050−1051. (c) Xiang, S.; Wu, X.; Zhang, J.; Fu, R.; Hu, S.; Zhang, X. J. Am. Chem. Soc. 2005, 127, 16352−16353. (d) Cheng, X.-N.; Zhang, W.-X.; Lin, Y.-Y.; Zheng, Y.-Z.; Chen, X.-M. Adv. Mater. 2007, 19, 1494−1498. (e) Wang, X.-Y.; Wang, Z.-M.; Gao, S. Chem. Commun. (Cambridge, U. K.) 2008, 281−294. (5) (a) Yin, Z.; Wang, Q.-X.; Zeng, M.-H. J. Am. Chem. Soc. 2012, 134, 4857−4863. (b) Mitzi, D. B.; Wang, S.; Field, C. A.; Chess, C. A.; Guloy, A. M. Science 1995, 267, 1473−1476. (c) Wang, S.; Mitzi, D. B.; Field, C. A.; Guloy, A. M. J. Am. Chem. Soc. 1995, 117, 5297−5302. (6) (a) Lin, W. J. Solid State Chem. 2005, 178, 2486−2490. (b) Xiong, R.; You, X.; Abrahams, B. F.; Xue, Z.; Che, C. Angew. Chem., Int. Ed. 2001, 40, 4422−4425. (c) Tian, G.; Zhu, G. S.; Yang, X. Y.; Fang, Q. R.; Xue, M.; Sun, J. Y.; Wei, Y.; Qiu, S. L. Chem. Commun. (Cambridge, U. K.) 2005, 1396−1398. (7) (a) Liu, D.; Ren, Z.-G.; Li, H.-X.; Lang, J.-P.; Li, N.-Y.; Abrahams, B. F. Angew. Chem., Int. Ed. 2010, 49, 4767−4770. (b) Zou, R.-Q.; Sakurai, H.; Han, S.; Zhong, R.-Q.; Xu, Q. J. Am. Chem. Soc. 2007, 129, 8402−8403. (c) Kitagawa, S.; Noro, S.-I.; Nakamura, T. Chem. Commun.(Cambridge, U. K.) 2006, 701−707. (d) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim, K. Nature 2000, 404, 982− 986. (8) (a) Rao, C. N. R.; Cheetham, A. K.; Thirumurugan, A. J. Phys.: Condens. Matter 2008, 20, 083202. (b) Han, L.; Hong, M.; Wang, R.; Luo, J.; Lin, Z.; Yuan, D. Chem. Commun.(Cambridge, U. K.) 2003, 2580−2581. (c) Zhou, Y.-F.; Hong, M.-C.; Wu, X.-T. Chem. Commun. (Cambridge, U. K.) 2006, 135−143. (9) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460−1494. (b) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem. Rev. 2003, 246, 247−289. (c) Batten, S. R.; Neville, S. M.; Turner, D. R. Coordination Polymers: Design, Analysis and Application; Royal Society of Chemistry: Cambridge, 2009. (10) (a) Sun, Q.; Wang, Y.-Q.; Cheng, A.-L.; Wang, K.; Gao, E.-Q. Cryst. Growth Des. 2012, 12, 2234−2241. (b) Wang, S.; Yun, R.; Peng, Y.; Zhang, Q.; Lu, J.; Dou, J.; Bai, J.; Li, D.; Wang, D. Cryst. Growth Des. 2012, 12, 79−92. (c) Li, D. S.; Ke, X. J.; Zhao, J.; Du, M.; Zou, K.; He, Q. F.; Li, C. CrystEngComm 2011, 13, 3355−3359. (d) Ma, L. Q.; Wu, C. D.; Wanderley, M. M.; Lin, W. B. Angew. Chem., Int. Ed. 2010, 49, 8244−8248. (e) Liang, L. L.; Ren, S. B.; Zhang, J.; Li, Y. Z.; Du, H. B.; You, X. Z. Dalton Trans. 2010, 39, 7723−7726. (f) Su, Z.; Fan, J.; Okamura, T. A.; Chen, M. S.; Chen, S. S.; Sun, W. Y.; Ueyama, N. Cryst. Growth. Des. 2010, 10, 1911−1922. (g) Ma, L. F.; Wang, L. Y.; Wang, Y. Y.; Batten, S. R.; Wang, J. G. Inorg. Chem. 2009, 48, 915− 924. (h) Carlucci, L.; Ciani, G.; Maggini, S.; Proserpio, D. M. Cryst. Growth Des. 2008, 8, 162−165. (i) Chen, Y.; Li, H.-X.; Liu, D.; Liu, L.L.; Li, N.-Y.; Ye, H.-Y.; Zhang, Y.; Lang, J.-P. Cryst. Growth Des. 2008, 8, 3810−3816. (11) (a) Limban, C.; Chifiriuc, M. C. Int. J. Mol. Sci. 2011, 12, 6432− 6444. (b) Lieffrig, J.; Yamamoto, H. M.; Kusamoto, T.; Cui, H.; Jeannin, O.; Fourmigué, M.; Kato, R. Cryst. Growth Des. 2011, 11, 4267−4271. (c) Zhang, Z.-H.; Chen, S.-C.; He, M.-Y.; Li, C.; Chen, Q.; Du, M. Cryst. Growth Des. 2011, 11, 5171−5175. (12) (a) Kasai, K.; Fujita, M. Chem.−Eur. J. 2007, 13, 3089−3105. (b) Kasai, K.; Aoyagi, M.; Fujita, M. J. Am. Chem. Soc. 2000, 122, 2140−2141. (c) Maspoch, D.; Domingo, N.; Ruiz-Molina, D.; Wurst, K.; Hernández, J. M.; Lloret, F.; Tejada, J.; Rovira, C.; Veciana, J. Inorg. Chem. 2007, 46, 1627−1633. (d) Gao, Y.; Twamley, B.; Shreeve, J. M. Inorg. Chem. 2006, 45, 1150−1155. (13) (a) Chen, S.-C.; He, M.-Y.; Yan, K.; Chen, Q.; Guo, Y.; Zhang, Y.-F. Inorg. Chem. Commun. 2007, 10, 451−454. (b) Chen, Q.; Chen,

ASSOCIATED CONTENT

S Supporting Information *

Experimental details, PXRD patterns, TGA curves, additional structural diagrams and tables, and crystallographic data (CCDC 918283−918286) for 1−4. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (Q. C); E-mail: dumiao@ public.tpt.tj.cn (M. D.). Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Grants 21201026 and 21031002), A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology (Grant BM2012110), and the Natural Science Fund for Colleges and Universities in the Jiangsu Province (Grant 12KJB150002).

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REFERENCES

(1) (a) Farha, O. K.; Hupp, J. T. Acc. Chem. Res. 2010, 43, 1166− 1175. (b) Liu, Y.; Xuan, W. M.; Cui, Y. Adv. Mater. 2010, 22, 4112− 4135. (c) Tranchemontagne, D. J. L.; Mendoza-Cortes, J. L.; O’Keeffe, M.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1257−1283. (d) Férey, G.; Serre, C. Chem. Soc. Rev. 2009, 38, 1380−1399. (e) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334−2375. (f) Janiak, C. Dalton Trans. 2003, 2781−2804. (g) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319−330. (h) Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629−1658. (2) (a) Roswell, J. L. C.; Yaghi, O. M. Angew. Chem., Int. Ed. 2005, 44, 4670−4679. (b) Zhang, J.-P.; Chen, X.-M. J. Am. Chem. Soc. 2008, 130, 6010−6017. (c) Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Science 2008, 319, 939−943. (d) Chen, B.; Zhao, X.; Putkham, A.; Hong, K.; Lobkovsky, E. B.; Hurtado, E. J.; Fletcher, A. J.; Thomas, K. M. J. Am. Chem. Soc. 2008, 130, 6411−6423. (e) Li, J.-R.; Tao, Y.; Yu, Q.; Bu, X.-H.; Sakamoto, H.; Kitagawa, S. Chem.Eur. J. 2008, 14, 2771−2776. (f) Ma, S.; Yuan, D.; Wang, X.-S.; Zhou, H.-C. Inorg. Chem. 2009, 48, 2072− E

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Crystal Growth & Design

Communication

S.-C.; Xiao, B.; Zhang, Z.-H.; He, M.-Y.; Yin, F.-H.; Du, M. Inorg. Chem. Commun. 2008, 11, 1371−1374. (c) Zhang, Z.-H.; Chen, S.-C.; Mi, J.-L.; He, M.-Y.; Chen, Q.; Du, M. Chem. Commun. 2010, 8427− 8429. (14) (a) Erxleben, A. Coord. Chem. Rev. 2003, 246, 203−228. (b) Jiang, P. J.; Guo, Z. J. Coord. Chem. Rev. 2004, 248, 205−229. (c) Carol, P.; Sreejith, S.; Ajayaghosh, A. Chem.−Asian J. 2007, 2, 338−348. (15) General experimental details are given in the Supporting Information. Complexes 1−4 were synthesized by the typical procedure as follows. Preparation of {[Zn 2 (H 2 tfpbbp) (tp)2(H2O)2]·2H2O}n (1): A mixture of H2tfpbbp (41.8 mg, 0.1 mmol), H2tp (16.6 mg, 0.1 mmol), and Zn(OAc)2·2H2O (22.0 mg, 0.1 mmol) was put into a Teflon-lined stainless steel vessel (20 mL) with 7 mL of water solvent. Then, the vessel was heated to 160 °C for 24 h and subsequently cooled to room temperature at a rate of 2 °C/h. Colorless block crystals were obtained in a 58% yield (27.5 mg, based on ZnII). (16) Single-crystal X-ray diffraction data collection was carried out on a Bruker Apex2 CCD-based X-ray diffractometer by using graphitemonochromated Mo Kα radiation (λ = 0.71073 Å). Crystal data for 1: triclinic, space group P1̅, a = 7.679(2), b = 8.747(2), c = 15.342(4) Å, α = 97.427(3), β = 97.273(3), γ = 106.380(3)°, V = 965.9(4) Å3, Z = 2, ρcalcd = 1.632 g cm−3, μ = 1.335 mm−1, 8562 reflections collected, 4353 independent reflections, R (all data) = 0.0396, wR (all data) = 0.0966, GOF = 1.106. Crystal data for 2: orthorhombic, space group Pna21, a = 18.241(4), b = 14.868(3), c = 19.410(4) Å, V = 5264.1(19) Å3, Z = 8, ρcalcd = 1.453 g cm−3, μ = 0.983 mm−1, 44848 reflections collected, 11844 independent reflections, R (all data) = 0.0492, wR (all data) = 0.1251, GOF = 1.033. Crystal data for 3: monoclinic, space group C2/c, a = 29.924(3), b = 10.8697(12), c = 18.562(2) Å, β = 116.496(1)°, V = 5403.4(10) Å3, Z = 8, ρcalcd = 1.792 g cm−3, μ = 0.897 mm−1, 22867 reflections collected, 6274 independent reflections, R (all data) = 0.0238, wR (all data) = 0.0643, GOF = 1.074. Crystal data for 4: monoclinic, space group C2/c, a = 29.757(9), b = 10.905(3), c = 18.485(6) Å, β = 115.391(3)°, V = 5419(3) Å3, Z = 8, ρcalcd = 1.610 g cm−3, μ = 0.864 mm−1, 22538 reflections collected, 6271 independent reflections, R (all data) = 0.0307, wR (all data) = 0.0867, GOF = 1.061. (17) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13. (18) Blatov, V. A.; Carlucci, L.; Ciani, G.; Proserpio, D. M. CrystEngComm 2004, 6, 377−395. TOPOS software is available for download at http://www.topos.ssu.samara.ru. (19) Ke, X. J.; Li, D. S.; Du, M. Inorg. Chem. Commun. 2011, 14, 788−803 and references therein. (20) (a) Li, C.-P.; Du, M. Inorg. Chem. Commun. 2011, 14, 502−513. (b) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem. Soc. Rev. 2009, 38, 1330−1352. (c) Hu, T.-L.; Zou, R.-Q.; Li, J.-R.; Bu, X.-H. Dalton Trans. 2008, 1302−1311. (d) Zou, R.-Q.; Bu, X.-H.; Zhang, R.-H. Inorg. Chem. 2004, 43, 5382−5386. (21) (a) Jiang, M.-X.; Zhan, C.-H.; Feng, Y.-L.; Lan, Y.-Z. Cryst. Growth Des. 2010, 10, 92−98. (b) Cai, L.-Z.; Chen, W.-T.; Wang, M.S.; Guo, G.-C.; Huang, J.-S. Inorg. Chem. Commun. 2004, 7, 611−613. (22) Chen, W.; Wang, J.-Y.; Chen, C.; Yue, Q.; Yuan, H.-M.; Chen, J.-S.; Wang, S.-N. Inorg. Chem. 2003, 42, 944−946.

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dx.doi.org/10.1021/cg4000445 | Cryst. Growth Des. XXXX, XXX, XXX−XXX