Article pubs.acs.org/IC
Construction of High-Nuclearity Manganese-Cluster−Organic Frameworks by Using a Tripodal Alcohol Ligand Xiang Ma,† Dan Zhao,‡ Li-Fen Lin,† Shao-Jie Qin,† Wen-Xu Zheng,† Yan-Jie Qi,† Xin-Xiong Li,*,† and Shou-Tian Zheng† †
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 cluster−organic frameworks based on the 12-nuclearity manganese-cluster secondary building unit (SBU), [MnIII4MnII8(L)4(Ac)8(MeO)2(μ5-O)2(H2O)4](Ac)2·16H2O (1) and [MnIII4MnII8(L)4(Ac)8(MeO)2(μ5O)2(H2O)4](Ac)2·12H2O (2), where Ac = CH3COO− and MeO = CH3O, have been constructed from solvothermal reactions of the 3-nuclearity manganese cluster [Mn3(μ3O)(Ac)6(py)3](ClO4) (Mn3, where py = pyridine) with a tripodal alcohol ligand containing a 4-pyridyl group. 1 and 2 represent the first examples of metal−organic frameworks containing 12-nuclearity manganese-cluster SBUs. In addition, 1 exhibits an integration of the porosity and magnetic properties from both the framework and cluster in a porous material.
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INTRODUCTION Metal−organic frameworks (MOFs) have attracted continuous scientific interest because of their fascinating structures, unique properties, and potential applications in gas storage, ion exchange, and magnetic materials.1 Their properties and performance are largely determined by the composition and structural characteristics of their inorganic nodes and organic linkers. Recently, the design and synthesis of MOFs from metal-cluster secondary building units (SBUs) have become a new research focus because such a method provides a new means to make novel cluster−organic frameworks with different functions. Compared with single metal ions, metal clusters usually possess larger sizes, high coordination numbers, rich coordination modes, and strong structure-directing functions. These advantages endow metal clusters with the ability to construct cluster−organic frameworks with more versatile, stable, and porous structures.2 Specifically, the introduction of metal clusters into MOFs can impart unique and intriguing physiochemical properties of clusters to the resulting frameworks. So far, great effort has been focused on this area, and a series of robust cluster−organic frameworks based on metal clusters such as Zn4O(CO2)6,3a Cu2(CO2)4,3b Zr6O4(OH)4(CO2)12,3c and In3O(CO2)33d have been successfully made.3 Compared with the above cluster−organic frameworks, the chemistry of manganese (Mn)-cluster−organic frameworks has also been studied. Polynuclearity Mn clusters constitute an intriguing class of potential SBUs for the preparation of multifunctional cluster−organic frameworks because the Mn © XXXX American Chemical Society
ion has unique electronic activity and magnetic properties as a result of its high-spin metal center and mixed-valence character. For example, a set of cluster−organic frameworks based on {Mn2},4a {Mn3},4b {Mn4},4c {Mn5},4d {Mn6},4e {Mn7},4f and {Mn10}4g SBUs have been successfully made in recent years. However, cluster−organic frameworks consisting of larger {Mnn} SBUs (n > 10) are very rare.5 High-nuclearity Mn clusters may possess a large-spin ground state and a negative axial anisotropy and may exhibit superparamagnetic properties.6 Therefore, the search for a suitable strategy to explore highnuclearity Mn-cluster−organic frameworks is an attractive but challenging goal.
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EXPERIMENTAL SECTION
In this work, we chose a tripodal alcohol ligand, 2-(hydroxymethyl)-2(pyridin-4-yl)-1,3-propanediol (H3L), as the functional ligand for the preparation of Mn-cluster−organic frameworks for the following reasons: (1) it is a rigid bifunctional ligand containing three hydroxyl groups and a 4-pyridyl group on the opposite end, enabling the L ligand to act as a linear bridge; (2) the three hydroxyl groups are often used as structure-directing agents to induce and stabilize in situ formed high-nuclearity Mn clusters;7 (3) the rigid 4-pyridyl groups provide remote coordination sites for neighboring high-nuclearity Mn clusters. As a result, extended cluster−organic frameworks containing highnuclearity Mn-cluster SBUs might be obtained. Herein, we report the synthesis, structures, and properties of two unprecedented cluster−organic frameworks, Received: August 5, 2016
A
DOI: 10.1021/acs.inorgchem.6b01857 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry [MnIII4MnII8(L)4(Ac)8(MeO)2(μ5-O)2(H2O)4](Ac)2·16H2O (1) and [MnIII 4MnII 8(L)4 (Ac)8(MeO)2(μ5-O)2 (H2O)4 ](Ac) 2·12H2O (2), where Ac = CH3COO− and MeO = CH3O, built from 12-nuclearity Mn-cluster SBUs. To the best of our knowledge, 1 and 2 represent the first examples of cluster−organic frameworks based on 12-nuclearity Mn-cluster SBUs, although many isolated {Mn12} clusters have been well studied in material sciences.8 Additionally, our synthetic strategy is different from those in references in which most reported Mncluster−organic frameworks are synthesized via reactions of MnII salts with organic ligands at present. 1 and 2 are synthesized by the solvothermal reactions of an isolated 3-nuclearity Mn-cluster, [Mn3(μ3-O)(Ac)6(py)3](ClO4) (Mn3; py = pyridine), with H3L (Scheme 1), which was rarely used to prepare Mn-cluster−organic
Scheme 1. Synthetic Route of 1 and 2a
a
(a) The 3-nuclearity Mn cluster [Mn3(μ3-O)(Ac)6(py)3]+. (b) The in situ generated Mn12 SBUs. The C atoms of the acetic groups and the methoxo ligands in part b are omitted for clarity.
frameworks.5c Compared with Mn2+, using the Mn3 cluster as the starting material may bring new possibilities to obtain larger clusters with high nuclearity because Mn3 clusters might not be stable enough and easily undergo self-aggregation or transformation in the solvothermal environment.5c Single-crystal X-ray structural analysis reveals that 1 and 2 contain the same 12-nuclearity mixed-valence Mn-cluster, {MnIII4MnII8(L)6(Ac)8(MeO)2(μ5-O)2(H2O)4} (Mn12; Figure 1a) SBUs, and exhibit a 3D extended framework and a 2D layer structure, respectively. The Mn12 cluster is made up of 12 Mn ions, six L ligands, eight acetic anions, two methoxo groups, and four terminal water ligands. In Mn12, there are six crystallographically independent Mn ions (Figure S1); two of them (Mn1 and Mn2) are trivalent and the rest (Mn3, Mn4, Mn5, and Mn6) are divalent, as confirmed by chargebalance considerations and bond-valence-sum (BVS) calculations (Table S1). With the exception of Mn5, which is seven-coordinate, all of the Mn ions are six-coordinate with distorted octahedral geometry. As shown in Figure 1b, Mn5 is surrounded by seven O atoms from three acetic groups and two L ligands. Mn4 is coordinated by six O atoms from one L ligand, one μ5-O atom, one methoxo ligand, and two acetic groups. Mn6 shows a coordination environment similar to that of Mn4 except that one acetic group was replaced by one terminal water ligand. Different from Mn5, Mn4, and Mn6, the coordination geometry of Mn3 contains one N atom of the L ligand, and its remaining five coordination sites are occupied by five O atoms from two L ligands, one acetic group, one methoxo ligand, and one terminal water molecule. The trivalent Mn1 is defined by four O atoms from two L ligands and two μ5-O atoms (Figure 1c). Mn2 adopts a semblable coordination style with Mn1 except that one μ5-O atom was substituted by one acetic group. The Mn−O bond distances are in the range of 1.916(3)−2.588(1) Å, and the Mn−N bond length is 2.240(5) Å. All four L ligands are fully deprotonated with two different types: two of them act as terminal ligands to coordinate with a Mn12 cluster through their hydroxyl groups, while the other four L ligands serve as bridge ligands. The methoxo ligands adopt a μ3-bridging mode. Peripheral ligation is provided by eight acetic groups exhibiting two binding modes: four bridge two Mn ions in the common syn,synμ-bridging mode, and the other four adopt a less common chelatebridging mode.9 Four terminal water ligands finally complete the coordination geometry of Mn3, Mn3a, Mn6, and Mn6a. BVS calculations performed on the O atoms confirmed the four water
Figure 1. (a) Ball-and-stick representation of the coordination environment of the Mn12 cluster in 1. (b) View of the structure of the {MnII4O17N} fragment. (c) View of the structure of the {MnIII4O16} unit. (d) Connection mode of the Mn12 cluster with the four neighboring ones. The H atoms in parts a and d and the C atoms in part b are omitted for clarity. Symmetry code: a, 1 − x, −y, 2 − z. Color code: MnIIO6, MnIIO5N, and MnIIO7, green; MnIIIO6, cyan. ligands. The structure of Mn12 can be described as a centrosymmetric {MnIII4O16} unit sandwiched by two {MnII4O17N} fragments through MnIII−O−MnII linkages (Figures 1b,c and S3). Notably, although the configuration of Mn12 in 1 is similar to those of reported discrete {Mn12} aggregates such as {MnIII4MnII8(L′)4(Ac)10(MeO)2(μ5O)2(H2O)2} [L′ = 1,1,1-tris(hydroxymethyl)ethane or 1,1,1-tris(hydroxymethyl)amine],8 the difference between Mn12 and reported discrete {Mn12} clusters is evident in the following aspects: (1) compared with reported discrete {Mn12} clusters, which are stabilized only by O-containing ligands, Mn12 comprises not only O-containing ligands but also N-donor pyridyl ligands; (2) reported {Mn12} clusters usually contain 10 carboxyl groups and two-coordinated water ligands in their periphery; however, the numbers of carboxyl groups and coordinated water molecules in Mn12 are 8 and 4, respectively. The most interesting structural feature is that 1 exhibits a 3D framework based on Mn12 SBUs, which is scarcely observed in Mncluster−organic frameworks. As shown in Figure 1d, each Mn12 cluster is connected to four neighboring ones through the sharing of four L ligands, leading to the formation of a 3D cationic framework (Figure 2). The framework possesses 1D six-membered channels with a diameter of about 2.0 nm along the c axis. The channels are occupied by guest solvent molecules, disordered charge-compensation anions, and uncoordinated pyridyl groups of L ligands, which are toward the center. From a topological point of view, the overall 3D framework can be rationalized as a four-connected NbO-type topology by assigning Mn12 clusters as nodes (Figure S3). The Schläfli symbol of this network is {64·82}. Adding of a small amount of Et3N to the reaction system led to the formation of another interesting cluster−organic framework, 2. In 2, B
DOI: 10.1021/acs.inorgchem.6b01857 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
Figure 4. Gas-sorption isotherms of 1. and 760 mmHg reach 50.86 and 75.29 cm3 g−1, respectively. The CO2 uptake capacity is comparable with that of the highly porous framework ZIF-82 (52.7 cm3 g−1; BET surface area = 1300 m2 g−1) under the same conditions,11 which is likely due to an important effect of the uncoordinated 4-pyridyl groups residing in the 1D channels.12 2 exhibits a type II isotherm, as confirmed by N2 absorption (Figure S7). The Langmuir and BET surface areas are 91.46 and 140.95 m2 g−1, respectively, which are much smaller than those of 1. The uptake capacities of N2 and H2 under 760 mmHg at 77 K reach 40.31 and 41.70 cm3 g−1, respectively. Further, CO2 sorption shows that 2 can absorb CO2 with a low uptake capacity of 13.98 cm3 g−1 under 760 mmHg at 273.15 K. The variable-temperature magnetic susceptibilities of 1 and 2 were measured in the temperature range of 2−300 K with an applied magnetic field of 1 kOe (Figure 5). The experimental χmT value of 1 and 2 at 300 K are 36.04 and 36.70 cm3 K mol−1, being much smaller than the theoretical value (47.00 cm3 K mol−1) expected for eight uncoupled high-spin MnII (S = 2.5) and four MnIII (S = 2.0) ions with g = 2.0. Upon cooling, the χmT values of 1 and 2 decrease smoothly to 21.81 cm3 K mol−1 at 42 K and 18 cm3 K mol−1 at 20 K. Upon cooling below 42 K, the χmT value of 1 exhibits a sharp rise, reaching a maximum of 23.18 cm3 K mol−1 at 34 K, and finally the χmT value again decreases to a minimum of 8.74 cm3 K mol−1 at 2 K. For 2, the χmT value shows a quick decrease to a minimum of 9.03 cm3 K mol−1 at 2 K upon cooling below 20 K. The above behaviors suggest the presence of dominant antiferromagnetic interactions within the clusters in both cases. The sharp drop in the χmT values of 1 and 2 below 34 and 20 K may be due to the magnetic field saturation effect.13,14 The temperature dependence of the reciprocal susceptibility (1/χm) obeys the Curie−Weiss law above 42 K for 1 and above 55 K for 2 with negative Weiss constant θ = −48.98 and −52.09 K (Figure 5), respectively, which further confirms the presence of antiferromagnetic interactions in both cases. The Curie constants C = 42.16 and 42.69 cm3 K mol−1 for 1 and 2, respectively, are also reasonable for 12 metal ions per formula unit. Field-dependent isothermal magnetization M(H) at 2 K shows a magnetization increase from 0 to 70 kOe, reaching 17.10 and 17.68 Nβ for 1 and 2 (Figure S8), which is lower than the saturation value Ms = 28 Nβ for eight MnII and four MnIII ions. This behavior could be attributed to the canted antiferromagnetic (AF) nature of the interaction between neighboring metal ions.15 Alternating-current magnetic susceptibilities for 1 and 2 with frequencies between 3 and 969 Hz were measured under an applied magnetic field of 1 kOe, and no frequency dependence are observed (Figure S9). The Mn···Mn exchange interactions in 1 and 2 are mainly mediated through μ2-O, μ3-O, and μ5-O bridges. The previous studies suggest that the magnetic coupling is highly sensitive to the values of the Mn−O−Mn bridging angles: the coupling is AF for angles larger than 90°.16 The
Figure 2. View of the 3D framework of 1 along the c axis, showing 1D channels. Color code: MnIIO6, MnIIO5N, and MnIIO7, green; MnIIIO6, cyan. each Mn12 SBU is connected by four symmetry-related ones, which are coplanar, leading to the formation of a novel 2D layer (Figure S4a). In each layer, the coordination connectivity between Mn12 SBUs generates parallelogram-shaped rings with the size of 1.62 × 0.50 nm. The 2D layers are further stacked in parallel with an −AAA− motif in the ab plane (Figure S4b) to form a 3D supramolecular framework (Figure 3).
Figure 3. View of the 3D supramolecular structure of 2. Color code: MnIIO6, MnIIO5N, and MnIIO7, green; MnIIIO6, cyan. The existence of the experimental powder X-ray diffraction (PXRD) patterns with the simulated ones based on single-crystal diffraction results indicated the good phase purities of 1 and 2 (Figure S5). The solvent-accessible volumes of 1 and 2, as estimated by the PLATON program,10 are about 48.6% and 25.9% of the total crystal volume, respectively. As shown in Figure 4, the N2 sorption of 1 exhibits a type I isotherm typical of a material of permanent porosity. The Langmuir and Brunauer−Emmett−Teller (BET) surface areas of 1 are 729.21 and 475.21 m2 g−1, respectively, and the median pore size is at 6.43 Å (Figure S6; using nonlocal density functional theory, NLDFT). Furthermore, 1 exhibits a significant uptake capacity for CO2 and H2. The CO2 uptake at 273 K and 760 mmHg and the H2 uptake at 77 K C
DOI: 10.1021/acs.inorgchem.6b01857 Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. 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 21303018, 21371033, 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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Figure 5. Temperature dependences of χmT and 1/χmT for 1 (top) and 2 (bottom).
cases in which the ∠Mn−O−Mn angles vary between 90.03(1) and 124.67(2)° in 1 and between 89.40(2) and 124.2(3)° in 2 exhibit that the dominant AF coupling is not unexpected. Actually, the AF exchange interactions of {Mn12} clusters were often encountered in the previous studies.8
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CONCLUSIONS
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ASSOCIATED CONTENT
REFERENCES
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In summary, we have successfully constructed two unprecedented cluster−organic frameworks based on Mn12 SBUs under solvothermal conditions. The Mn12 SBUs are generated in situ from the reported 3-nuclearity Mn-cluster Mn3. The deliberate choice of bifunctional ligand H3L is crucial for the synthesis of these cluster−organic frameworks. What’s more, the frameworks of 1 and 2 exhibit an integration of the porosity and magnetic properties from both the framework and cluster in one porous material. These results further demonstrate that the search for high-nuclearity metal clusters as SBUs is an effective method in making porous functional materials. Further work based on Mn clusters with higher nuclearity is in progress.
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b01857. Experimental details, crystallographic data for 1, additional structural figures, and additional characterizations such as PXRD patterns, etc. (PDF) D
DOI: 10.1021/acs.inorgchem.6b01857 Inorg. Chem. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.inorgchem.6b01857 Inorg. Chem. XXXX, XXX, XXX−XXX
