An Anionic Uranium-Based MetalâOrganic Framework with Ultralarge

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An Anionic Uranium-Based Metal–Organic Framework with Ultra Large Nano-Cages for Selective Dye Adsorption Falu Hu, Zhengyi Di, Peng Lin, Pan Huang, Mingyan Wu, Feilong Jiang, and Maochun Hong Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01525 • Publication Date (Web): 04 Jan 2018 Downloaded from http://pubs.acs.org on January 5, 2018

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Crystal Growth & Design

An Anionic Uranium-Based Metal–Organic Framework with Ultra Large Nano-Cages for Selective Dye Adsorption Falu Hu,ab# Zhengyi Di,ac# Peng Lin, ab Pan Huang,ab Mingyan Wu,*a Feilong Jiang,a Maochun Hong*a a

State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the

Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China b

University of the Chinese Academy of Sciences, Beijing, 100049, China

c

College of Material Science and Engineering, Fujian Normal University, Fuzhou,

350007, China. Abstract: We herein present a rarely-seen (3,4)-connected non-interpenetrated anionic uranium-organic framework with tbo topology (FJI-H-U1), which is constructed from two kinds of ultra large nano-cages. More importantly, FJI-H-U1 can selectively adsorb positively charged organic dyes EV, JB and RB over anionic organic dye MO due to the nature of its anionic framework.

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The chemistry of uranium is currently witnessing a speeding up of its historical process owing to the diverse charming structures and various applications, such as ion exchange, gas storage and separation, photochemical catalysis, photoelectronic effects and nonlinear optics.1-8 Over the past two decades, a large number of efforts have been made to build the 0D clusters, 1D chains and 2D layers of uranium complexes.9-13 However, the 3D uranium-organic frameworks (UOF) are quite rare, especially for the compounds with ultra large pore structures.14-21 The main reason may be attributed to the linear geometry of the uranyl ion UO22+ in the axial direction, which restricts the incoming carboxylic ligand to only bonding to the U(VI) centre at the equatorial plane, forming the planar triangular [UO2(COO)3]- units. Due to the lack of extension along the axial direction, uranyl coordination complexes usually tend to form the chain-like or sheet-like structures rather than the 3D porous networks, especially when the planar or rigid organic ligands are utilized.22,23 The flexible multidentate ligands tend to form 3D networks because they can extend the structures along not only the equatorial plane but also the axial direction of the U(VI) ion through the nonplanar conformations of the ligands. Thus, the rational selection of the organic ligand was essentially important to build 3D UOF. On the other hand, as we know that the high connected porous 3D UOFs with large cages have been rarely reported,24 because porous frameworks normally tend to form the interpenetrated structures,25,26 which can block the porous structure. According to the previously reported topology structure, the (3,4)-connected tbo net topologically can preclude the interpenetration of the framework and leave the large pores.27 Considering that the planar triangular [UO2(COO)3]- units could be simplified to the 3-connected node, if we rationally choose a square ligand to ligate to the U(VI) cation as the 4-connected node the (3,4)-connected non-interpenetrated tbo network would be obtained. Bearing the above idea in mind, we choose the tetrakis(4-carboxyphenyl)ethylene (H4TCPE) as the organic ligand because it can serve as the 4-connected linker. Additionally, according to the references reported the C-C bonds of H4TCPE ligands can rotate freely between four arms and ethylene core to give a nonplanar conformation, which


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may be helpful to construct 3D UOF. Herein, we report a non-interpenetrated 3D tbo UOF, which exhibits the selective dye adsorption. Mixture of H4TCPE and (UO2)(NO3)2·6H2O in N,N-dimethylformamide (DMF) with trifluoroacetic acid (TFA) under solvothermal conditions yielded light yellow cubical crystals of FJI-H-U1. Single crystal structure analysis reveals that FJI-H-U1 is in the cubic space group Fm-3m and the asymmetric unit comprises one-sixth of UO22+ cation, one-eighth of TCPE4- ligand and some disordered guest molecules as well as counter cations residing inside the anionic framework. Figure 1a shows that the coordination geometry of each U(VI) ion is an ideal hexagonal bipyramidal with six oxygen atoms from three chelating carboxylate groups located at the equatorial plane and two uranyl oxygen atoms in the axial positions, forming a negatively charged [UO2(COO)3]- unit. The surrounding environment of the U(VI) cation defines the hexagonal bipyramidal geometry with the average U-O distance of 2.46 Å and U=O bond of 1.75 Å, which are in good agreement with those of uranium-organic frameworks reported.28 As anticipated, in the TCPE4- ligand the four outer phenyl rings are not coplanar and are all perpendicular to the inner ethylene core. Therefore, the triangular [UO2(COO)3]- unit and the TCPE4- ligand are also not coplanar with the dihedral angle of 90°, which is critical for the construction of 3D uranium-organic framework. In FJI-H-U1, each UO22+ unit bridges three TCPE4- ligand as a 3-connected node and each TCPE4- ligand is linked to four neighbouring [UO2(COO)3]- SBUs as a 4-connected node. Subsequently, FJI-H-U1 was analysed by the TOPOS 4.0 program package,29 exhibiting a desired tbo topology with the point symbol of {6^2.8^2.10^2}3·{6^3}4 (Figure 2b). A particularly salient feature of FJI-H-U1 is that it is constructed from two kinds of cavities, i.e. small octahedral cages and large cubooctahedral cages. As shown in Figure 1c, the small cage consists of four UO22+ cations and six half TCPE4- ligands to form an octahedron-like cage. As shown in Figure S1, the



centroids of the ethylene cores reside at each vertex of the octahedron respectively. The four uranium centres are located at the centres of the four triangular planes respectively, with a distance of 10.96 Å between two neighbour U(VI) ions. The triangular window of the octahedral cage is estimated as c.a. 15.55 Å x15.55 Å x 15.55 Å from the separations of centroids of the ethylene cores (Figure S2a). Such large window can allow the big guest molecules such as dye molecules to go in / out of the octahedral cage freely. The large cubooctahedral cage is surrounded by twenty-four UO22+ and twelve TCPE4- ligands (Figure 1d). This large cage has two kinds of windows, i.e. small triangular window and large square window. The small window is as the same as the triangular one in the octahedral cage. The size of large window is ca. 14.89 Å x 14.89 Å, which is much larger than that of the triangular window (Figure S2). This cubooctahedral cage is very similar to the classical one, which is constructed from twelve dinuclear copper(II) paddle wheels and twenty-four isophthalic acid ligands.30 However, since the TCPE4- ligand is longer than isophthalic acid, the size of this U(VI) cage is much larger than that of the Cu24 cage. The diameter of the U(VI) cage is estimated as 31.10 Å by the separations of the two opposite carbon atoms of the ethylene cores, while the diameter of the Cu24 cage is estimated as 16.06 Å by the separations of the two opposite Cu(II) ions. Further analysis of the structure reveals that each cubooctahedral cage is connected by eight octahedral cages and six cubooctahedral cages through eight triangular windows and six square windows respectively. Upon packing, these two kinds of cages form a 3D porous structure, which is interconnected through the large-size triangular and / or square windows. Compared with the polynuclear actinyl peroxide nanospheres,31 FJI-H-U1 exhibits larger cavities and apertures, which can be attributed to the large organic ligand in UOFs. Meanwhile, according to the references reported, complexes with large cavities constructed by H4TCPE and d-block ions are also seldom observed.32-37 To our best knowledge, the cavities in FJI-H-U1 are among the largest ones in the reported UOFs.3, 24-26 The calculated void space38 ACS Paragon Plus Environment

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in FJI-H-U1 (without counterions) is approximately 85.5%, which is larger than those of many other porous or interpenetrated UOFs.39,40 Considering the charge of the skeleton within FJI-H-U1, three kinds of cationic organic dyes, Ethyl Violet (EV), Janus Green B (JB), Rhodamine B (RB), and one kind of anionic dye, Methyl Orange (MO), were chosen as diagnostic agents to investigate the adsorption of guest molecules.41,42 The reason is that not only these four kinds of dyes are suitable for pore permeation in the structure but also their large UV/Vis absorption extinction coefficients are able to facilitate the detection and quantification of their uptake by FJI-H-U1. Identical amounts (5 mg) of freshly prepared crystals of FJI-H-U1 were soaked in the solution of these organic dyes at room temperature. The UV/Vis absorbance of dyes was monitored after 0, 1, 6, 13 and 20h. As shown in Figure 3a, 3b, and 3c, the concentrations of the cationic organic dyes EV, JB and RB obviously decrease with time, which indicates that they can be efficiently adsorbed by FJI-H-U1. Meanwhile, the yellow crystals of the FJI-H-U1 gradually became purple, blue and pink respectively (Figure S4). According to the standard curves for EV, JB and RB, 78.2%, 87.4%, 63.3% of dyes concentration can be absorbed by crystals of FJI-H-U1 after 20h respectively. As comparison, the experiment of anionic organic dye MO was also carried out. However, the curves of the UV/V is spectrum have no obvious change even after 20 hours, which shows that there is almost no adsorption of the anionic organic dye MO (Figure 3d). In addition, FJI-H-U1 has no obvious adsorption of the neutral dyes (Figure S7). The above results exhibit that the FJI-H-U1 could selectively adsorb organic cationic dyes. In order to test the cycle performance of FJI-H-U1, we have done three cycles of the experiments for absorption and desorption of the cationic dye molecules (Figure S6). The above results indicate that the cycle performance of FJI-H-U1 is also good.43 In order to further validate the selective separation performance of FJI-H-U1, competition experiments were performed. Mixing equimolar



amounts of cationic dye (EV, JB and RB respectively) and anion dye MO in solution results in the corresponding purple, blue, pink solutions, which are then transferred to the vials containing 5mg FJI-H-U1, respectively. The UV/Vis spectra show that the cationic dyes can be effectively adsorbed, while the absorbance of the MO dye is almost no obvious change (Figure 4). At the same time, the colours of the solutions change from purple, blue and pink to yellow over 20h (Figure S5), indicating that cationic dyes can be selectively adsorbed over anionic organic by crystals of FJI-H-U1. These distinctive results suggest that the dye adsorption by the anionic FJI-H-U1 may be driven by the cation–cation exchange effect. In conclusion, an non-interpenetrated porous uranium-organic framework with the desired tbo topology has been successfully prepared by combining the triangular D3h-symmetry [UO2(RCOO)3]- units with a square-like tetracarboxylate organic ligand. A particularly salient feature of this complex is that it is constructed from two kinds of ultra large cavities. Owing to the high porosity and the nature of anionic framework, FJI-H-U1 can selectively adsorb positively charged organic dyes over the negatively charged dye. This result opens up the exploration of potential applications of UOFs. Further work will devote to the design and fabrication of UOFs by combining [UO2(COO)3]- SBUs with high-symmetry ligands and the exploration of their potential applications. ACKNOWLEDGEMENTS This manuscript is dedicated to Prof. Xin-Tao Wu on the occasion of his 80th birthday. We acknowledge the financial supports of the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), 973 Program (2014CB932101 and 2013CB933200), National Nature Science Foundation of China (21390392 and 21731006), Key Research Program of Frontier Science CAS (QYZDY-SSW-SLH025), Youth Innovation Promotion Association CAS, and Chun miao Project of Haixi Institutes (CMZX-2016-001). SUPPORTING INFORMATION


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X-ray crystal data of FJI-H-U1 (CCDC 1575362), detailed experimental procedures, crystal data and additional figures. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author E-mail: [email protected]; [email protected]. Author Contributions #

These authors contributed equally.

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For Table of Contents Use Only An Anionic Uranium-Based Metal–Organic Framework with Ultra Large Nano-Cages for Selective Dye Adsorption Falu Hu, Zhengyi Di, Peng Lin, Pan Huang, Mingyan Wu,* Feilong Jiang, Maochun Hong*

We herein present a rarely-seen (3,4)-connected non-interpenetrated anionic uranium-organic framework with tbo topology (FJI-H-U1), which is constructed from two kinds of ultra large nano-cages. More importantly, FJI-H-U1 can selectively adsorb positively charged organic dyes EV, JB and RB over anionic organic dye MO due to the nature of its anionic framework.



Figure 1 (a) The [UO2(COO)3]- SBU. (b) The fully deprotonated TCPE4- ligand. (c) and (d) Two different kinds of cages in FJI-H-U1. The inner cavities are displayed by the purple and yellow spheres respectively. (d) The relative position of the small cage and the large cage. For clarity, the hydrogen atoms are omitted. 263x464mm (300 x 300 DPI)


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Figure 2. (a) The 3D porous non-interpenetration structure of FJI-H-U1 upon packing. (b) The (3,4)connected tbo-topology. Green node, 3-connected [UO2(COO)3]- SBU; Purple node, 4-connected TCPE4ligand. 87x172mm (220 x 220 DPI)



Figure 3. UV/Vis spectra of CH3CH2OH solutions of (a) Ethyl Violet (EV), (b) Janus Green B (JB), (c) Rhodamine B (RB) and (d) Methyl Orange (MO) in the presence of FJI-H-U1 with time. 129x111mm (300 x 300 DPI)


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Figure 4. The selective adsorption capability of different dyes RB + MO (a), EV + MO (b), and JB + MO (c) in the presence of FJI-H-U1 with time. 120x97mm (300 x 300 DPI)


An Anionic Uranium-Based MetalâOrganic Framework with Ultralarge

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