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By using the bifunctional organic ligand Hina as a linker, two new heterometallic organic frameworks based on trinuclear indium and cuprous halide clu...
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Heterometallic Organic Frameworks Built from Trinuclear Indium and Cuprous Halide Clusters: Ligand-Oriented Assemblies and Iodine Adsorption Behavior Jin-Hua Liu,† Yan-Jie Qi,† Dan Zhao,‡ Hao-Hong Li,*,† and Shou-Tian Zheng*,†

Inorg. Chem. 2019.58:516-523. Downloaded from pubs.acs.org by UNIV OF LOUISIANA AT LAFAYETTE on 01/07/19. For personal use only.

†

State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China ‡ Fuqing Branch of Fujian Normal University, Fuqing, Fujian 350300, China S Supporting Information *

ABSTRACT: Two novel heterometallic organic frameworks built from trinuclear indium and cuprous halide clusters, [(In3O)2(Cu2I2)3(ina)12(H2O)6](NO3)2·7DMA·10H2O (1) and [NH2(CH3)2][In3(OH)2(H2O)2(ina)8(Cu4I4)2]·5DMA· 8H2O (2), where Hina = isonicotinic acid, have been successfully constructed with the orientation of the ina ligand. 1 shows a fascinating highly porous honeycomb-like 3D cationic framework with a trigonal-bipyramid-type cage based on a planar [In3O(CO2)6]+ trimer and a rhombohedral Cu2I2 cluster. Comparably, 2 displays a 3D negative network with irregular hexagonal channels constructed from a [In3(OH)2(CO2)8]− trimer and a cubane-like Cu4I4 cluster. Especially, 1 displays a reversible I2 adsorption/release performance with high adsorption capacity, whose mechanism has been disclosed by theoretical simulation. Also, the green/red emission of 2 stems from iodocuprate centers with quenched indium-centered emission.

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INTRODUCTION Cluster-based organic frameworks have emerged as a hot field in recent years because of their unique physical/chemical properties and wide applications including gas adsorption, conductivity, magnetism, and photochemistry.1 Especially, some cluster-based organic frameworks can exhibit good performance of radioactive I2 molecule adsorption, which might be significant for environmental purification.2 With regard to their structures, the rigid metal clusters could serve as high-connectivity nodes with specific geometry structures, and the configuration of the final product is much more predictable rationally. To date, a large number of cluster-based organic frameworks built from a square-paddlewheel [Cu2(CO2)4] cluster, a trianglar [In 3 O(CO 2 ) 3 ] cluster, a linear [Mg3(COO)6] cluster, an octahedral [Zn4O(CO2)] cluster, a cubane-like Cu4I4 cluster, a pentanuclear [Co5(μ3-OH)2] cluster, a dodecahedral [Zr6O4(OH)4(CO2)12] cluster, and a cubic [ZnI8] cluster have been successfully prepared via directional self-assembly approaches.3 However, heterometallic organic frameworks containing two distinct clusters have been far less explored.4 Generally speaking, diverse metal clusters may show various structural roles and different coordination behaviors, for © 2018 American Chemical Society

instance, radii, coordination geometries, and preferences for donating atoms. One common strategy for the preparation of heterometallic cluster-based organic frameworks is the usage of pyridyl nitrogen-donor and carboxylate oxygen-donor organic ligands as linkers and distinct metal ions according to hard− soft acid−base (HSAB) theory.5 Hitherto, compared with the extensive research on transition-metal (copper, zinc)-based heterometallic organic frameworks, indium-cluster-bearing framework research is still relatively scarce.6−9 Experimentally speaking, In3+ ions exhibit flexible coordination geometries and tend to form 4-connected {In(O2CR)4} clusters,6 {In(OH)} chains,7 and 6-connected {In3O(O2CR)6(H2O)3} clusters.8 To date, the triangular {In3O(O2CR)6(H2O)3} cluster has been broadly employed in building cluster-based organic frameworks. Earlier, Eddaoudi and co-workers used In(NO3)3·5H2O and 1,3-benzenedicarboxylic acid to obtain two novel metal− organic frameworks (MOFs) based on {In3O(O2CR)6(H2O)3} secondary building units (SBUs).8a Bu et al. succeeded in constructing an unparalleled In12@In24 cage-based porous material, which was proven to be a potential candidate for gas Received: September 25, 2018 Published: December 14, 2018 516

DOI: 10.1021/acs.inorgchem.8b02734 Inorg. Chem. 2019, 58, 516−523

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Figure 1. (a) Simplified trigonal configuration of [In3O(CO2)6]. (b) Simplified planar quadrilateral Cu2I2 cluster. (c) Connectivity of the Cu2I2 cluster with four [In3O(CO2)6] moieties.

storage.8b More recently, Hong’s group also reported a series of InOF.9 Besides, among different forms of metal ions or metal clusters, copper iodide clusters, Cu+-based units, are so nitrogen-affinitive centers. So far, Cu+-based units have exhibited versatile structural motifs such as Cu2I2, Cu3I4, Cu4I4 Cu6I6, Cu8I6, and Cu8I8, some of them have been used in the building of heterometallic organic frameworks. For instance, using Cu2I2 and [Ti6O6][iPrO]66+ clusters as SBUs, giant sodalite cages with 3D open square channels can be constructed.10 Similarly, coordination cages built from Cu4I4 and [Zr6(μ3-OH)8(OH)8]8+ SBUs have been achieved by Yuan’s group.11 Moreover, heterometallic organic frameworks based on indium clusters have exhibited good gas storage/ separation performances, and cuprous halide clusters have represented specific luminescence properties.8,12 Up to now, only one heterometallic MOF based on indium clusters and copper iodides has been reported.13 Therefore, the heterometallic MOFs constructed from indium and copper iodide clusters remain at the beginning. Recently, two types of isomorphic indium-based heterometallic organic frameworks built by 1,3,5-benzenetricarboxylic acid and imidazole-4,5dicarboxylic acid have been synthesized in our gourp.14,15 Herein, we designed and synthesized two novel heterometallic cluster-based organic frameworks built from trinuclear indium and cuprous halide clusters, i.e., [(In3O)2(Cu2I2)3(ina)12(H2O)6](NO3)2·7DMA·10H2O (1) and [NH2(CH3)2][In3(OH)2(H2O)2(ina)8(Cu4I4)2]·5DMA· 8H2O (2). Interestingly, 1 displays a 3D cationic skeleton, which is built from a planar [In3O(CO2)6] trimer and a rhombohedral Cu2I2 cluster. However, 2 displays a 3D negative framework, which is constructed from a [In3(OH)2(CO2)8]− trimer and a cubane-like Cu4I4 cluster. The band gaps are 2.026 and 2.444 eV for 1 and 2, respectively, suggesting their semiconductive nature, and the luminescence properties of 2

have been investigated. Especially, 1 exhibits impressive I2 adsorption/release properties.

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RESULTS AND DISCUSSION Synthesis. Objected compounds 1 and 2 were generated from the reaction of In(NO3)3·4.5H2O, CuI, and Hina with the presence of different additive agents. The powder X-ray diffraction (PXRD) patterns, IR, and thermal stabilities of 1 and 2 are investigated (Figures S9−S11). For 1, when methyl viologen is replaced by tetrabutylammonium, crystals 1 can also be obtained, but the yield is lower and the phase purity is poorer. Tetrabutylammonium is a frequently used phasetransfer catalyst. However, in this system, methyl viologen acting as a phase-transfer catalyst is more effective, which was essential for the pure phase and high yield of 1. In 2, the pH of the reaction solution is 4.4 without the presence of 5nitroisophthalic acid. However, the pH can be lowered to 4.0 after the addition of a specific amount of 5-nitroisophthalic acid, and only under this pH condition can crystal 2 be obtained. Furthermore, if 5-nitroisophthalic acid is replaced with similar 1,3-dicarboxybenzene or 5-aminoisophthalic acid, the pH is higher than 4.0 and no products can be prepared. So, the conclusion could be drawn that 5-nitroisophthalic acid might serve as a special pH adjustor. Additionally, during our exploration, we found that the solvent N,N′-dimethylacetamide (DMA) and temperature (100 °C) are crucial during the crystallization process of 1 and 2. When N,N′-dimethylformamide (DMF), N,N′-dibutylformamide, N-methylformamide, or N,N′-diethylformamide were used to replace DMA as the solvent, no products of 1 and 2 can be obtained. When the synthesis temperatures are far from 100 °C (for example, 80 or 120 °C), lower yields, worse morphologies, and crystal qualities will be achieved. Structural Description of 1. According to structural analysis, 1 belongs to a hexagonal system with space group 517

DOI: 10.1021/acs.inorgchem.8b02734 Inorg. Chem. 2019, 58, 516−523

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Inorganic Chemistry P3̅m1, which is built by rhombohedral Cu2I2 and [In3O(CO2)6]+ trimer molecular building blocks. The independent unit consists of half an In3+ ion, one-fourth of the Cu2I2 dimer, one ina− ligand, one-sixth of the μ3-O2− anion, and half a terminally coordinated H2O (Figure S1). The In3+ center is surrounded by six donors, among which four oxygen atoms stem from COO− of four ina− ligands, the other two donors are μ3-O2− species and H2O. Three In3+ atoms and the μ3-O2− atom are coplanar with an average In−μ3-O distance of 2.097 Å and an In−μ3-O−In angle of 120°, leading to trimer molecular building block [In3O(CO2)6] (Figure 1a). The planar [In3O(CO2)6] moiety is defined by six COO− from six ina− ligands. This structure consists of a [In3O(CO2)6] cluster and an ina− ligand, which is similar to the structures of the MIL-88 and MIL-101 series.16 The bifunctional ina− ligand also links to a conventional cuprous iodide cluster. The Cu+ center is in tetrahedral geometry, two CuI2N2 tetrahedra are linked by two μ2-I− to give a Cu2I2 cluster (Figure 1b). Therefore, the rhombohedral Cu2I2 is saturated geometrically by four pyridyl groups from four ina− ligands to form a 4connected [Cu2I2N4] moiety, which further links four [In3O(CO2)6]+ clusters to the present heterometallic MOF (Figure 1c). In the rhombohedral Cu2I2 and trimer [In3O(CO2)6] clusters, the In−O and Cu−N/I distances are in the normal ranges. A prominent structural feature in 1 consists of trigonalbipyramid-type cages made up of Cu2I2 clusters, [In3O(CO2)6]+ clusters, and Hina ligands (Figure 2b). Each cage contains three Cu2I2 clusters and two [In3O(CO2)6] clusters

connected by six Hina ligand linkers, resulting in an inner sphere of approximately 12 Å diameter and a pore volume of about 7234.56 Å3. Each of these cages is surrounded by five adjacent cages via a face-sharing mode (Figure 2c). It is noteworthy that the pore volume ratio of this framework is 79.7%, as calculated from PLATON. A honeycomb-like 3D cationic network is shaped with the coexistence of Cu2I2 and [In3O(CO2)6]+ clusters bridged by Hina, in which a large 1D hexagonal channel (23.0 × 23.0 Å2) along the c direction is given (Figure 2a,d). Furthermore, along the a/b axis, the distances between neighboring [In3O(CO2)6] and Cu2I2 clusters are around 11.68 and 13.76 Å, and 1D rhombus channels formed cluster by cluster are presented (Figure S3). NO3− ions act as counteranions for charge balance of the cationic framework of 1. To our knowledge, 1 exhibits the large channels among the MOFs based on cuprous halide clusters, which is larger than those of JLU-Liu14 based on Cu2I2 clusters (the dimensions of 14 × 14 Å2 and 5 × 5 Å2)2a and [(Cu2I)Cu2L2(H2O)2]22+·2NO3−·5DMF based on the [Cu2I]n chain (the dimensions of 13.3 × 4.7 Å2 and 6.7 × 4.0 Å2).2c Topologically, the Cu2I2 clusters can be treated as 4connected nodes, and [In3O(CO2)6] clusters serve as 6connected nodes. Consequently, 1 adopts a 4,6-connected network, which can be depicted as {4^4.6^2}3{4^9.6^6}2 using the Schlafli symbol (Figure 2e). The connection between indium clusters and copper iodides generates a highly porous honeycomb-like 3D cationic framework, which is similar to that of the first heterometallic MOF, InOF-8.13 However, 1 is still somewhat disparate from InOF-8. The angle between indium and cuprous halide clusters defined by the nitrogen atom, pyridine ring center of the ligand, and oxygen atom of the indium cluster is used to discuss their structural differences (Figure S4). These angles differ greatly with values of 178.15° and 115.99° for 1 and InOF-8, respectively. Consequently, 1 forms a larger hexagonal window (20.21 Å) than InOF-8 (13.02 Å) in the c-axis direction (Figure S5). Structural Description of 2. 2 crystallizes in the orthorhombic system with space group Pbcn, and its asymmetric unit consists of one and a half crystallographically unique In3+ ions, one Cu4I4 cluster, four ina− ligands, one OH−, and one H2O (Figure S6). Similarly, the structural features of 2 lie in its incorporation of two different types of metal clusters. The first is a linear trinuclear indium cluster, which includes two independent In3+ ions (In1 and In2). In1 at the center of the trinuclear indium cluster is situated on a special position, which is in a distorted octahedral configuration with six oxygen donors: four oxygen donors originate from four ina− ligands, and two donors are OH− anions (Figure 3a,b). Two other equivalent terminal In2 atoms locate on general positions and are also in distorted octahedral environments. The difference lies in a coordinated H2O compared with that of In1. Afterward, one In(1)O6 and two In(2)O6 octahedra are combined into a trimer via a vertexsharing model. To date, such linear trinuclear [M3(COO)6] (M = Zn, Ni, Mn, Cd) clusters have been documented.17 However, such a linear trinuclear indium cluster is rare in InM O F , a n d o n l y o n e I n - M O F b a s e d o n l i n e ar [In3(CO2)6(OH)4] SBUs was reported.18 The second kind of cluster is a typical Cu4I4 cubane (Figure 3c), which can be further linked by four pyridinyl nitrogen atoms from four independent ina− ligands (Figure S7).

Figure 2. (a) Hexagonal channels of 23.0 × 23.0 Å2 along the a axis. (b and c) Trigonal-bipyramid-type cages. (d) Polyhedral view of a honeycomb-like 3D structure running along the c axis. (e) Topological representation for 1. 518

DOI: 10.1021/acs.inorgchem.8b02734 Inorg. Chem. 2019, 58, 516−523

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smaller free volume than that of 1, which is calculated as 18959.6 Å3 per unit cell volume and 69.8% porosity after the removal of gust molecules. The charge of the framework is negative, which is balanced by the decomposition product of DMA, NH2(CH3)2+.19 Topologically, the Cu4I4 cluster serves as a 4-connected node, and the trinuclear indium cluster acts as a 8-connected node, so 2 can be simplified as a binodal 4,8connected net with the Schlafli symbol of {4^6}2{4^9.6^18.8} (Figure 3e,f). According to HSAB theory, the bifunctional organic ligand Hina contains both nitrogen and oxygen donors, which could coordinate to different metal centers selectively. In this work, In3+ ions are COO−-affinitive and Cu+ ions N-affinitive, based on which novel heterometallic organic frameworks can be generated. Therefore, these two heterometallic organic frameworks can also be clarified as ligand-oriented assemblies. 1 and 2 are constructed from by a bifunctional Hina linker, cuprous halide clusters with neutral units act as 4-connected nodes, the [In3O(CO2)6]+ and [In3(OH)2(CO2)8]− trimers serve as 6and 8-connected nodes, respectively. Notably, 1 and 2 illustrate that different indium-based clusters carry different charges; for example, the [In3O(CO2)6]+ and [In3(OH)2(CO2)8]− trimers have In3+/COO− ratios of 3/6 and 3/8, respectively. For 1, the [In3O(CO2)6]+ cluster-ligated neutral unit is usually predicted to synthesize porous cationic frameworks. Although porous cationic MOFs have been explored for several applications such as anion exchange (Cr2O72−, MnO4−, and TcO4−),20 their use as adsorbents for radioactive I2 molecule capture is still relatively scarce. For 2, the [In3(OH)2(CO2)8]− clusters connected with neutral units may be used to construct negative frameworks. Furthermore, 2 represents the first case of a heterometallic organic framework containing a linear trimer [In3(OH)2(CO2)8]− cluster as the SBU. Iodine Adsorption and Desorption Experiments. Considering the larger cavities and positive charges of the heterometallic framework in 1, I2 adsorption and release experiments have been executed. In the I2 adsorption experiments, 100 mg of fresh sample was soaked in a 0.01

Figure 3. (a and b) Schematic illustrations of a linear trinuclear indium [In3(CO2)6(OH)4] cluster. (c) Connectivity around the Cu4I4 cluster. (d) 1D irregular hexagonal channel with the size of 20.2 × 13.1 Å2. (e) Polyhedral view of the 3D framework along the a axis. (f) Representation showing the topologies of the 3D framework for 2. Each [In3(OH)2(CO2)8]− trimer cluster as a 8-connected node and Cu4I4 cluster as a 4-connected node.

Interestingly, in the whole framework, trinuclear indium clusters are linked together by eight COO− from eight ina− ligands, and they can further be linked by cubane-like Cu4I4 clusters to generate a 3D negative network with irregular hexagonal channels of 20.2 × 13.1 Å2 along the c axis (Figures 3d and S8). According to PLATON calculations, 2 shows a

Figure 4. (a and b) Pictures of different time intervals the I2 adsorption/release process in 10 mL of cyclohexane and CH3OH, respectively. (c and d) Crystal morphology of 1 before and after I2 adsorption under an optical microscope. 519

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donated I in the Cu2I2 cluster. Finally, the large channels in 1 support the I2 high adsorption capacity. Optical Absorption Spectra. The room temperature UV−vis diffuse-reflectance spectra of 1 and 2 were recorded so as to determine their photophysical properties (Figure S15). The band gaps evaluated from the equation αhν2 = K(hν − Eg)1/2 are 2.026 and 2.444 eV for 1 and 2, respectively,23 showing their potential semiconductors.24 Both 1 and 2 exhibit a broad adsorption zone from 200 to 550 nm, which are probably assigned to the ligand-to-copper center charge transfers and d−d transitions of CuI ions.25 However, in 2, a near-IR adsorption located among 700−800 nm can be observed, which could be assigned to charge transfer from the anion skeleton to the NH2(CH3)2+ cation. The distinction of the absorption spectra is also consistent with their different crystal colors (Figure S16). Photoluminescent Properties. The photoluminescence behaviors have been investigated at both room and low temperature (77 K). Unfortunately, the color of 1 is darker, and no photoluminescence can be observed. When excited at 401 nm (Figures 6 and S17), 2 shows a typical emission at 588

mol/L cyclohexane solution of I2 at room temperature. The I2 solution shows an obvious color change from dark red to pale red (Figure 4a); meanwhile, the crystals slowly change their color from orange to dark brown after 24 h (Figure 4c,d). The IR spectra of compound 1 before and after I2 adsorption also confirm the presence of I2 in the lattice (Figure S10a). The mass of compound 1 after adsorption increases by ca. 45 wt %, which could be associated with a maximum adsorption of 6.07 I2 per formula unit. This value is superior to that of a cuprous halide based organic framework such as JLU-Liu15.2d In order to look further into the I2 release kinetics, UV−vis measurements on samples at different time intervals were conducted. The I2 concentration change was determined by the intensity variation of I2 and polyiodide I3− at 220, 291, and 360 nm, respectively.21 As shown in Figure 4, 1 mg of I2@1 with dark-brown crystals was soaked in 10 mL of CH3OH, a color change from colorless to pale yellow of the CH3OH solution was observed, and the crystals became orange. The photographs and UV−vis spectra for I2@1 demonstrate that the I2 adsorption/release process is reversible (Figure 5). The

Figure 5. UV−vis spectra of a CH3OH solution soaked with I2@1. Figure 6. Emission spectra of 2 at 297 and 77 K.

release of I2 is a gentle process, with an average rate of 1.154 × 10−4 mg/mL (4.7 × 10−7 mol/L), and 0.14 mg of I2 was released from crystals of I2@1 after 100 min according to the standard curve (Figures S12 and S13). The crystal framework of 1 is still retained after I2 adsorption/release according to the PXRD patterns (Figure S9). In order to disclose the iodine adsorption/release mechanism, theoretical calculations based on the density functional theory method were conducted. The mode was constructed from the CIF file of 1, and the included solvents were removed. According to Hall’s theory, the Imol−Ianion bond in the I3− anion is a dative bond rather than a covalent bond.22 So, the Imol− Ianion bond strength is weak and can dissociate easily, and, furthermore, the dissociation and formation Imol−Ianion bond is reversible. Therefore, during the adsorption/release process, I2 molecules were adsorbed onto the bridged I of the Cu2I2 cluster to generate a stable Cu2I−I3− clusters (Figure S14). The adsorption energy calculated from Eads = Eframework+I2 − (Eframework + EI2) was −3.64 eV, indicating a weak chemical adsorption. These adsorption energies also suggest that reversible adsorption/release is feasible, which is consistent with the experimental results. The weaker Imol−Ianion bond than the normal I3− anion should be led by the bridged nature of

nm at 77 K, which is similar to previously reported cuprous halide cluster complexes.26 With the temperature rising to 298 K, a sharp decrease of the emission intensity and an obvious red shift (588 → 626 nm) of the emission maximum can be observed (Figure 6).27 Moreover, a distinct emission stemming from the indium center is not found. Emission of the indium center can frequently be observed at about 400−450 nm.28 In the heterometallic organic framework of 2, emission of the indium cluster was adsorbed because the excited wave locates in this zone. Therefore, the emission bands could be assigned to (1) a “Cu4I4 cluster-centered” triplet excited state, which includes both the Cu4 and I4 tetrahedral units and (2) the mixed excited states combining iodide-to-metal charge transfer with “metal-cluster-centered“ (d10 Cu → d9s1 Cu) transfer.29 Therefore, the tunable luminescence of 2 stems from iodocuprate centers at 298 and 77 K in the solid state. Such changes in the location and intensity of the emission peaks could be judged from the fact that the Cu−Cu distance becomes shorter and the bonding character increases as the temperature decreases.30 520

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CONCLUSIONS In summary, by adopting the bifunctional organic ligand Hina as a linker, two new heterometallic cluster-based organic frameworks built from trinuclear indium and cuprous halide clusters have been successfully obtained. 1 displays a highly porous honeycomb-like 3D heterometallic MOF with the coexistence of Cu2I2 and [In3O(CO2)6]+ clusters, in which a large hexagonal channel of diameter 23.0 Å and small trigonalbipyramid-type cage along the c axis can be observed. 2 represents a rare example of a heterometallic cluster organic framework containing Cu4I4 and [In3(OH)2(CO2)8]− clusters. Furthermore, 1 displays high I2 adsorption and release capacity. These results can further enrich the structural diversities of indium/cuprous halide cluster heterometallic frameworks, and the strategy in this work can provide a valuable and promising approach to the preparation of unique heterometallic cluster-based organic frameworks.

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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b02734. Additional experimental details, crystallographic data and structure refinements for 1 and 2 (Table S1), and structural figures and characterizations for complexes 1 and 2 (PDF) Accession Codes

CCDC 1866406−1866407 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

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Hao-Hong Li: 0000-0003-3543-7715 Shou-Tian Zheng: 0000-0002-3365-9747 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundations of China (Grants 21371033, 21671040, and 21401195), the Natural Science Foundation for Young Scholars of Fujian Province (Grant 2015J05041), and Projects from State Key Laboratory of Structural Chemistry of China (Grants 20150001 and 20160020).

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REFERENCES

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