Mixed Short and Long Ligands toward the Construction of Metal

Communication Cite This: Cryst. Growth Des. 2019, 19, 3120−3123

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Mixed Short and Long Ligands toward the Construction of Metal− Organic Frameworks with Large Pore Openings Published as part of a Crystal Growth and Design virtual special issue on Crystalline Functional Materials in Honor of Professor Xin-Tao Wu Chao Zhuo, Fei Wang,* and Jian Zhang*

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State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China S Supporting Information *

ABSTRACT: Short azole and long tris(4-(1H-imidazol-1yl)phenyl)amine (Tipa) ligands are incorporated into the syntheses of metal−organic frameworks (MOFs) for the first time. Owing to the discovery of a binary solvothermal reaction system, a short−long azole mixing strategy is realized. By this strategy, a cationic MOF possessing a large pore opening (maximum size 13.1 Å) is obtained with permanent porosity and ion-exchange property. Also, another cationic one with a rare sandwich layer can be obtained when using tetrazole instead of imidazole under a similar reaction condition. The slight difference between imidazole and tetrazole is amplified by Zn-Tipa into disparate frameworks. S1).23−26 However, no N-coordinated colinkers have been reported before. On the basis of this strategy, we reported here the syntheses of two MOFs, namely, [Zn3(Tipa)2(Im)3]·3NO3·solvent (1, Im = imidazole) with a three-dimensional (3D) pillared-layer framework and [Zn2(Tipa)2(Tz)][Zn(Tipa)(NO3)(H2O)]· 4NO3·3DOA·solvent (2, Tz = tetrazole, DOA = 1,4-dioxane) with a rare sandwich structure. Compound 1 with a large pore opening exhibits permanent porosity and Cr2O72− ionexchange properties. Interestingly, in compound 2, Tipa and Tz ligands linked Zn atoms generating a double layer structure, which is interpenetrated by a Zn-Tipa single layer. The slight difference between imidazole and tetrazole is amplified by Tipa into these totally disparate frameworks. X-ray Crystallography. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the Pnma space group of the orthorhombic system. The smallest asymmetric unit contains one and a half Zn2+ ions, one and a half imidazole, one Tipa molecule, and a half dissociative NO3− ion. Two different occupied Zn2+ centers share the same tetrahedral coordination geometry with two N sites from each Tipa and two N sites from each imidazole (Figure 1a). Tipa connects Zn2+ as a three-dentate ligand in the three-petalshaped layer (Figure 1b,c), while imidazole bridges adjacent Zn2+ making the pillars (Figure 1d). However, these pillars are arranged in a zigzag way. Each Zn atom is linked by Tipa and

Because of structural similarity with zeolites, porous metal− organic frameworks (MOFs) with low connectivity and azole ligands, called metal−organic zeolites (MOZs) as well, have attracted much research interest.1−3 Including typical zeolite imidazole frameworks (ZIFs) and boron imidazole frameworks (BIFs), these materials are a balance between the designability and stability of the framework.4−12 Compared to zeolites, the introduction of organic ligands into the structure of MOZs gives an opportunity to construct porous frameworks with higher porosity and larger pore openings. Two main strategies have been developed to achieve the goal. The first one is the link−link interaction.13−16 For example, various substitute groups and their different positions on the azole rings play an important role in the final topologies of ZIFs whose largest pore opening reaches 22.5 Å.16 The second one is the structure direct agent method (SDA) or template method.17,18 Such strategies are undoubtedly successful in structure diversity, but the aimed large pore openings cannot be steadily obtained. In principle, it is reliable to use longer linkers to synthesize MOFs with larger pore openings.19 On the basis of this consideration, we reported here a new way to construct metal− organic frameworks (MOFs) by mixing the short azole and long tris(4-(1H-imidazol-1-yl)phenyl)amine (Tipa) ligands for the first time. Different from the above strategies, the imidazole derivative Tipa is chosen as an auxiliary for azoles because it is an adaptable neutral ligand with terminal imidazole groups to coordinate metal ions.20−22 There are dozens of examples that Tipa participates in MOF constructions so far, either by itself or with inorganic anions and carboxylates as colinkers (Table © 2019 American Chemical Society

Received: March 29, 2019 Revised: May 6, 2019 Published: May 16, 2019 3120

DOI: 10.1021/acs.cgd.9b00426 Cryst. Growth Des. 2019, 19, 3120−3123

Crystal Growth & Design

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Figure 1. (a) Coordination environment of Zn in compound 1. (b) Coordination mode of Tipa. (c) Tripetal-shaped layer of Tipa and Zn. (d) Zig-zag pillar of imidazole and Zn. (e) Pillar-layer topology. (f) Framework similar to a Chinese lantern. All H atoms are omitted for clarity.

Figure 2. (a) Coordination environment of Zn in compound 2, part one. (b) Coordination environment of Zn in compound 2, part two. (c) Bilayer framework of part one. (d) Monolayer framework of part two. (e) Sandwich topology of bilayer and monolayer. (f) View of the host−guest structure, dissociate NO3− (sky blue) and DOA (black). All H atoms are omitted for clarity.

Im ligands to generate a 3D pillared-layer framework. Looking down along the a axis, the framework is like a Chinese lantern (Figure 1f). The dissociative NO3− is located in the lantern’s central elliptic channel whose diameters are ca. 7.7 and 13.1 Å. Other disordered ones are not identified. The whole framework can be simplified as a (3,4,4)-connected network with a point symbol {6.82}2{64.8.10}2{85.10} (Figure 1e).27 The replacement of imidazole with tetrazole during the reaction gives compound 2 as a result. Different from compound 1, it crystallizes in the triclinic system with P1̅ space group. The smallest asymmetric unit is made of two main unconnected parts. In part one, two Zn2+ cations are both in tetrahedral coordination geometry (Figure 2a). Each Zn2+ is connected by three Tipa molecules to construct a layer that is further bridged by tetrazole through Zn2+ sites to form a bilayer structure (Figure 2c). In part two, Zn2+ is found to be trigonal−bipyramid coordinated (Figure 2b). The three coordination sites in the plane are occupied by N atoms from each Tipa, while the axial sites are occupied by two O atoms from water and nitrate ion, thus making a monolayer (Figure 2d). Overall, the part-two monolayer is sandwiched and fixed in the part-one bilayer (Figure 2e,f). Each part has honeycomb-shaped pore openings with a diameter of ca. 11.0 Å, which decreases to 7.8 Å because of interpenetration. Besides, dissociative NO3− and DOA fill in the pores (Figures 2f and S1). As discussed above, compounds 1 and 2 can be prepared in similar conditions, except for imidazole for 1 and tetrazole for 2, respectively. On the basis of our many synthesis experiments, the coordination ability of Tipa is stronger than that of both imidazole and tetrazole in normal solvent systems, leading to the specific structures with only Tipa. The ability of imidazole and tetrazole is not even close to that of Tipa until a DOA/water binary solution was found. And the slight structural difference between imidazole and tetrazole leads to totally different frameworks. In addition, oxygen bridges often exist in Tipa-involved MOFs obtained from an alkaline

reaction system. However, by adjusting the pH in this DOA/ water reaction system, azole ligands will take place of them in situ. Coincident with previous research, the angle of the neighboring Zn−imidazole bond is around 145° in compound 1. In comparison, that of neighboring Zn-tetrazole is around 162° in compound 2. And these −1 charged linkers slightly reduce the electropositivity, helping to stabilize the frameworks. It is worth mentioning that the two parts in compound 2 direct each other to form the unique sandwich structure, and the interaction between them forces the Zn2+ in part two to adopt a rare trigonal−bipyramid coordination. Gas Adsorption. Considering the good performance of azole-related MOFs in CO2 absorption, the gas adsorption properties of both compounds were fully investigated. Powder X-ray diffraction (PXRD) patterns revealed that both of the compounds were stable after solvent exchange (Figures S5 and S6). However, thermogravimetric analysis (TGA) of compound 2 showed that conventional solvent exchange was not available for it (Figure S4), though it had a 32.6% void ratio slightly larger than 28.8% for compound 1 according to PLATON calculation.28 Furthermore, its framework collapsed after activation at 50 °C and the BET experiment, while compound 1 survived these processes. The N2 adsorption of compound 1 measured at 77 K showed type I sorption isotherms and took up N2 to 43.3 cm3/ g (Figure S7). The corresponding BET surface area was 128.6 m2/g. A single data point at a relative pressure of 0.016 gave a maximum pore volume of 0.059 cm3/g by the Horvath− Kawazoe equation. Its CO2 adsorption was 55.4 cm3/g at 273 K and 52.7 cm3/g at 290 K, respectively (Figure 3a). In comparison, compound 2 showed poor adsorption ability to 3121

DOI: 10.1021/acs.cgd.9b00426 Cryst. Growth Des. 2019, 19, 3120−3123

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both N2 and CO2 even after 100 °C activation, corresponding to the PXRD result (Figures S7 and S8).

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.9b00426. Experimental details, structural picture, IR spectra, TGA diagram, powder X-ray diffraction, gas adsorption diagram, and UV−vis absorption spectra (PDF) Accession Codes

CCDC 1906174−1906175 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*(F.W.) E-mail: [email protected]. *(J.Z.) E-mail: [email protected]. ORCID

Fei Wang: 0000-0001-8432-0009 Jian Zhang: 0000-0003-3373-9621 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We acknowledge the support of this work by NSFC (21573236). Figure 3. (a) CO2 adsorption of compound 1 at 273 and 290 K. (b) Intensity changes of UV−vis spectra of K2Cr2O7 aqueous solution at a maximum absorption wavelength after compound 1 was added in, and those of the release process for compound 1 collected in a previous step in KNO3 aqueous solution.

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DOI: 10.1021/acs.cgd.9b00426 Cryst. Growth Des. 2019, 19, 3120−3123