Cluster-Based Anionic Template Assisted in the Formation of 3D

Zhang, Z.; Zhang, L.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Template-Directed Synthesis of Nets Based upon Octahemioctahedral Cages That Encapsul...
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Cluster-Based Anionic Template Assisted in the Formation of 3D Cobalt Cationic Framework: A Bridge Connecting MOFs and Halometallates? Song-De Han, Di Wang, Jie Pan, Qi Wei, Jin-Hua Li, and Guo-Ming Wang* College of Chemistry and Chemical Engineering, Qingdao University, Shandong 266071, China

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metal−organic complexes (metalloporphyrins, [M(2,2′-bipy)x]y+ cations), inorganic compounds (iodine, polyoxometalates), gas molecules (CO2), and surfactants.22 It is found that the charge of most of the explored templates is cationic or neutral. By contrast, MOFs directed by the anionic template are few.22 Therefore, it is necessary to enlarge the scope of the available template via introducing the anionic template to suitable cationic MOF systems, considering the tailorability and tunability of MOFs. To achieve this goal, we first turned our attention to the cationic MOFs with neutral rigid polydentate N-ligands as linkers and transition-metal cations as nodes because their network could be predesigned by reticular chemistry.30,31 The charge of cationic MOFs is usually compensated by the anions from the corresponding metal salts thanks to the neutral Nligands. The next and significant step is to choose a suitable anionic template to substitute simple counterions from the reactants metal salts. Considering the anionic and lowdimensional characteristics of the iodocuprate family, it is feasible to introduce proper iodocuprate complexes as a template to cationic MOFs to direct the synthesis of novel inorganic−organic hybrids (iodocuprate@MOFs) with captivating structures or properties. On the basis of these aforementioned thoughts, we attempted to explore the CoO-tib (1,3,5-tris(1-imidazolyl)benzene)-CuI-HI, taking into account the following features: (a) The use of CoO as a metal source could allow us to avoid the introduction of additional anions. (b) tib, as a neutral triimidazole ligand, could readily coordinate to cobalt ions to form cationic MOF. (c) HI could not only in situ react with CoO to release Co(II) and I− but also prompt the solubility of CuI via in situ forming anionic iodocuprate complexes. We, herein, report a cationic MOF, [Co(tib)2]·[Cu4I6] (1), templated by anionic discrete iodocuprate (CuI4I62−). 1 features a (3,6)-connected network with Co(II) and tib moieties as six- and three-connected nodes, respectively. The visible-light-driven photocatalytic property of 1 has also been investigated. The space group for 1 is cubic Pa-3. There are three crystallographically independent units in the asymmetric unit, including one Co(II) cation, one neutral tib unit, and one anionic [CuI4I6]2− guest with oriented disorder (Figure S1 in the Supporting Information). The Co1(II) ions feature an

ABSTRACT: The marriage of metal−organic framework (MOF) and metal halide gives birth to a novel 3D cationic MOF, [Co(tib) 2 ]·[Cu 4 I 6 ] (1, tib = 1,3,5-tris(1imidazolyl)benzene), templated by anionic iodocuprate cluster (CuI4I62−). 1 features a (3,6)-connected network with CoII and tib moieties as six-connected and threeconnected nodes, respectively. It is notable that the template (iodocuprate cluster) in 1 is distinct from the widely utilized species such as organic solvents, ionic liquids, organic amines, and surfactants. This Communication provides a new avenue to fabricate halometallatedirected MOF via incorporating halometallate into MOF. The photocatalytic activity toward the degradation of methyl orange in aqueous solution under visible-light irradiation has also been studied.

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etal−organic frameworks (MOFs) generated from the assembly of metal ions (or metal clusters) and organic linkers have emerged as a versatile hybrid with widespread applications in assorted domains such as adsorption, separation, luminescence, catalysis, magnetism, drug delivery, and so on.1−14 From the point of fundamental research, the construction of MOFs driven by new synthetic methodology could greatly push the development of corresponding synthetic chemistry and structural chemistry, promoting the investigation of potential structure-related properties.15−21 Among the various synthetic methods toward novel MOFs, the template-directed synthesis of MOFs has been intensively explored and well summarized, which could give us a better comprehension of the nature of intermolecular interactions between the template and the resulting host frame.22−27 The template-directed synthetic method could act as a toolkit for the generation of MOFs that cannot be accessible without the use of a template. For example, the famous HKUST-1 is composed of [Cu2(RCOO)4(H2O)2] paddlewheels and 1,3,5benzenetricarboxylate (BTC);28 however, the direct assembly of corresponding cobalt(II) salt (or manganese(II) salt) with H 3 BTC under similar conditions could not generate isostructural HKUST-1-M (M = Co, Mn). Indeed, the Co/ Mn analogs of HKUST-1 were fabricated by employing a template-directed synthesis strategy.29 According to the nature of template, the templates in the template@MOFs structure are divided into six classifications, which are solvent (organic solvent, ionic liquids), organic compounds (amines, N-heterocyclic aromatic compounds), © XXXX American Chemical Society

Received: July 19, 2018

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DOI: 10.1021/acs.inorgchem.8b02030 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

three- and six-connected nodes, respectively. The final cationic MOF features a (3,6)-connected network with the point symbol of (612·83)(63)2 (Figure 1d) calculated by TOPOS.33 Notably, the charge of the cationic frame is compensated by the disordered tetrahedral [CuI4I6]2− moieties (Figure 1b and Figure S1 in the Supporting Information), which exist in the cavity of the frame and interact with the cationic architecture via electrostatic interaction (Figure 1c). Compared with the common tetranuclear halocuprate clusters bearing cubane, stepped cubane, and open cubane structure, the tetrahedral counterpart is very rare.34 Different from the reported cationic tib-based MOFs with a simple anion (OH−, SO42−, ClO4−, Br−, NO3−) as counterion,35−41 1 displays a 3D (3,6)connected net with the complicated [CuI4I6]2− cluster as counterion. The counter-anions are mainly from the metal salts in the reported tib-based MOFs. By contrast, the iodocuprate clusters in 1 are in situ generated and introduced into cationic MOF system, which may be more likely to act as a template.22 Compared with the broadly investigated organic template and inorganic−organic hybrid template in the fabrication of MOFs,22 investigations of the reported inorganic template (iodine and polyoxometalates, CO2) are few. Therefore, it is impending to broaden the scope of the available inorganic template. To our knowledge, the inorganic iodocuprate cluster was first introduced into MOF, yielding the [CumIn]−(n−m)@ MOFs hybrids. Considering the structural diversity of the iodocuprate cluster (or halometallates) and the predesign nature of MOFs driven by reticular chemistry, we could construct a bridge between halometallates and MOFs to afford novel hybrid materials (halometallate-directed MOFs). Thermogravimetric (TG) charactrization was conducted to study the thermal stability of 1. There is no obvious weight loss before 400 °C in the TG plot (Figure S2 in the Supporting Information). Further heating leads to an apparent and continuous weight loss between 430 and 1000 °C, which implies the collapse of the frame and the combustion of constituents. As shown in Figure S3 in the Supporting Information, 1 features bright blue luminescence with a maximum band at ∼350 nm upon excitation at 280 nm. Compared with the luminescence emission of the tib ligand, the maximum of luminescence emission of 1 displays a slight blue shift. The emission of 1 may be mainly ascribed to the ligand-centered π−π* transition. In general, a small band gap is required for some photoelectric materials, especially for visiblelight photocatalytic materials. The optical diffuse reflectance spectrum shows an absorption edge at ∼540 nm, corresponding to the yellow appearance of the crystals (Figure S4 in the Supporting Information). The band gap derived from the Tauc plot was 2.29 eV (Figure S5 in the Supporting Information),42 which is closely matched to the initial absorption photon energy of the absorption edge. Recent studies have demonstrated that MOFs and cuprous halides are promising candidates for photocatalytic degradation of organic pollutants.43−46 Considering the structural characteristics of 1 together with the narrow band gap of 1, we studied its photocatalytic activities. We choose MO (methyl orange) as the test pollutant for degradation experiment. There is almost no reduction in concentration with time, and the degradation is almost negligible without catalyst or light irradiation. 1 could decompose ∼50% of MO after 20 min and 80% of MO after 100 min (Figure 2a,b). The color of the solution gradually became colorless, indicative of the degradation of MO.

octahedral coordination mode finished by six symmetry-related N atoms from six tib ligands (Figure 1a). Each tib ligand acts

Figure 1. (a) Coordination modes of Co(II) and tib. (b) Disordered anionic iodocuprate cluster. (c) Anionic iodocuprate cluster guest@ cationic host frame. (d) (3,6)-Connected cationic network.

Figure 2. (a) Photocatalytic degradation of MO under visible-light irradiation at ambient temperature. (b) UV−vis absorption plot of MO.

as a [3.111]-bridging mode to connect three symmetry-related Co1(II) ions (Figure 1a).32 From the topological point, the neutral tib ligands and Co(II) cations could be viewed as B

DOI: 10.1021/acs.inorgchem.8b02030 Inorg. Chem. XXXX, XXX, XXX−XXX

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(4) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to Metal− Organic Frameworks. Chem. Rev. 2012, 112, 673−674. (5) Gao, Q.; Xu, J.; Cao, D.; Chang, Z.; Bu, X. H. A Rigid Nested Metal-Organic Framework Featuring a Thermoresponsive Gating Effect Dominated by Counterions. Angew. Chem., Int. Ed. 2016, 55, 15027−15030. (6) Zhao, J. P.; Xu, J.; Han, S. D.; Wang, Q. L.; Bu, X. H. A Niccolite Structural Multiferroic Metal−Organic Framework Possessing Four Different Types of Bistability in Response to Dielectric and Magnetic Modulation. Adv. Mater. 2017, 29, 1606966. (7) Long, J. R.; Yaghi, O. M. The pervasive chemistry of metalorganic frameworks. Chem. Soc. Rev. 2009, 38, 1213−1214. (8) Gao, Q.; Xu, J.; Bu, X.-H. Recent advances about metal−organic frameworks in the removal of pollutants from wastewater. Coord. Chem. Rev. 2018, DOI: 10.1016/j.ccr.2018.03.015. (9) Doonan, C. J.; Sumby, C. J. Metal-organic framework catalysis. CrystEngComm 2017, 19, 4044−4048. (10) Zhou, H.-C.; Kitagawa, S. Metal−Organic Frameworks (MOFs). Chem. Soc. Rev. 2014, 43, 5415−5418. (11) Liu, X.-J.; Zhang, Y.-H.; Chang, Z.; Li, A.-L.; Tian, D.; Yao, Z.Q.; Jia, Y.-Y.; Bu, X.-H. A Water-Stable Metal−Organic Framework with a Double-Helical Structure for Fluorescent Sensing. Inorg. Chem. 2016, 55, 7326−7328. (12) Chen, Q.; Feng, R.; Xu, J.; Jia, Y.-Y.; Wang, T.-T.; Chang, Z.; Bu, X.-H. Kinetic and Thermodynamic Control of Structure Transformations in a Family of Cobalt(II)−Organic Frameworks. ACS Appl. Mater. Interfaces 2017, 9, 35141−35149. (13) Chang, Z.; Yang, D.-H.; Xu, J.; Hu, T.-L.; Bu, X.-H. Flexible Metal−Organic Frameworks: Recent Advances and Potential Applications. Adv. Mater. 2015, 27, 5432−5441. (14) Feng, R.; Jia, Y.-Y.; Li, Z.-Y.; Chang, Z.; Bu, X.-H. Enhancing the stability and porosity of penetrated metal-organic frameworks through the insertion of coordination sites. Chem. Sci. 2018, 9, 950− 955. (15) Wu, M.-M.; Wang, J.-Y.; Sun, R.; Zhao, C.; Zhao, J.-P.; Che, G.B.; Liu, F.-C. The Design of Dual-Emissive Composite Material [Zn2(HL)3]+@MOF-5 as Self-Calibrating Luminescent Sensors of Al3+ Ions and Monoethanolamine. Inorg. Chem. 2017, 56, 9555−9562. (16) Zhao, J.-P.; Han, S.-D.; Jiang, X.; Xu, J.; Chang, Z.; Bu, X.-H. A three dimensional magnetically frustrated metal-organic framework via the vertices augmentation of underlying net. Chem. Commun. 2015, 51, 4627−4630. (17) Guan, H.-Y.; LeBlanc, R. J.; Xie, S.-Y.; Yue, Y. Recent progress in the syntheses of mesoporous metal−organic framework materials. Coord. Chem. Rev. 2018, 369, 76−90. (18) Ren, J.; Dyosiba, X.; Musyoka, N. M.; Langmi, H. W.; Mathe, M.; Liao, S. Review on the current practices and efforts towards pilotscale production of metal-organic frameworks (MOFs). Coord. Chem. Rev. 2017, 352, 187−219. (19) Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chem. Rev. 2012, 112, 933−969. (20) Rubio-Martinez, M.; Avci-Camur, C.; Thornton, A. W.; Imaz, I.; Maspoch, D.; Hill, M. R. New synthetic routes towards MOF production at scale. Chem. Soc. Rev. 2017, 46, 3453−3480. (21) Julien, P. A.; Mottillo, C.; Friscic, T. Metal-organic frameworks meet scalable and sustainable synthesis. Green Chem. 2017, 19, 2729− 2747. (22) Zhang, Z.; Zaworotko, M. J. Template-directed synthesis of metal-organic materials. Chem. Soc. Rev. 2014, 43, 5444−5455. (23) Wang, Z.-M.; Hu, K.-L.; Gao, S.; Kobayashi, H. Formate-Based Magnetic Metal-Organic Frameworks Templated by Protonated Amines. Adv. Mater. 2010, 22, 1526−1533. (24) Li, K.; Lin, S.-L.; Li, Y.-S.; Zhuang, Q.-X.; Gu, J.-L. AqueousPhase Synthesis of Mesoporous Zr-Based MOFs Templated by Amphoteric Surfactants. Angew. Chem., Int. Ed. 2018, 57, 3439−3443. (25) Chen, D.-M.; Zhang, N.-N.; Liu, C.-S.; Du, M. Templatedirected synthesis of a luminescent Tb-MOF material for highly

To further confirm the photocatalytic activities of 1, we also investigated the photocatalytic degradation of MO of reactants. The results indicated that more than 94% (for CoO), 90% (for CuI), and 92% (for tib) of MO molecules are unconverted under similar conditions. There is no apparent loss of photodegradation efficiency after three cycles (Figure S6 in the Supporting Information). The PXRD (power X-ray diffraction) patterns of the recovered samples matched those of the initial samples (Figure S7 in the Supporting Information), suggesting that 1 maintains its structural integrity after photodegradation experiment. In summary, we report a novel cationic MOF templated by discrete iodometallate, which features a (3,6)-connected network with Co(II) and tripodal imidazole moieties as sixand three-connected nodes, respectively. The visible-lightdriven photocatalytic degradation of MO has also been studied. It is notable that the template (iodometallate cluster) in this work is different from the widely utilized species such as organic solvents, ionic liquids, organic amines, and surfactants. This work provides new insights into synthesizing halometallate-directed MOFs (halometallate@MOFs) via merging anionic halometallates into cationic MOFs. Further investigation of hybrid materials based on MOFs and halometallates is in progress.

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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.inorgchem.8b02030. Experimental section, supplementary structural figure, additional characterization data, and table (PDF) Accession Codes

CCDC 1847043 contains 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 Author

*E-mail: [email protected]. ORCID

Song-De Han: 0000-0001-6335-8083 Guo-Ming Wang: 0000-0003-0156-904X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We acknowledge the grants from the Natural Science Foundation of China (21571111, 21601099). REFERENCES

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DOI: 10.1021/acs.inorgchem.8b02030 Inorg. Chem. XXXX, XXX, XXX−XXX