Tuning the Topology from fcu to pcu: Synthesis and Magnetocaloric

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Tuning the Topology from fcu to pcu: Synthesis and Magnetocaloric Effect of MOFs Based on a Hexanuclear Gd(III)-Hydroxy Cluster Wei Wei, Xue Wang, Kai Zhang, Chong-Bin Tian, and Shao-Wu Du Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01566 • Publication Date (Web): 06 Dec 2018 Downloaded from http://pubs.acs.org on December 8, 2018

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Crystal Growth & Design

Tuning the Topology from fcu to pcu: Synthesis and Magnetocaloric Effect of MOFs Based on a Hexanuclear Gd(III)-Hydroxy Cluster Wei Wei, †,§ Xue Wang,┴ Kai Zhang, †,§ Chong-Bin Tian,*† and Shao-Wu Du*‡ †

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

Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China ‡

Center for Advanced Marine Materials and Smart Sensors, Minjiang University, Fuzhou,

Fujian 350108, P. R. China §

University of Chinese Academy of Sciences, Beijing, 100049, P. R. China

┴

Yantai Branched Center of Shandong Technology Transfer Center, Chinese Academy of

Sciences, Shandong, Yantai 264000, P. R. China

ACS Paragon Plus Environment

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Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT: Two polynuclear cluster-based MOFs, formulated as {H2[Gd6(OH)8(H2O)6(pBDC-F4)6]·3(2,2′-bpy)·6H2O} (1) and {H2[Gd6(OH)8(H2O)6(m-BDC-F4)6]·3(4,4′-bpy)·6H2O} (2) (p-BDC-F4 = tetrafluoroterephthalic acid, m-BDC-F4 = tetrafluoroisophthalic acid), are synthesized by hydrothermal reactions of GdIII ions with perfluorinated benzenedicarboxylate. Structure analysis illustrate that both 1 and 2 are constructed by hexanuclear GdIII-hydroxy cluster molecular building block {Gd6(OH)8(COO)12(H2O)6}, generating a 12-connected fcuMOF and a 6-connected pcu-MOF, respectively. Compounds 1 and 2 are stable in some refluxing organic solvents, boiling water, as well as aqueous solutions in the pH range of 2‒11. Notably, magnetic investigation indicates that 1 and 2 display a significant magnetocaloric effect.

During the past decades, investigation of magnetic cooling materials that have giant magnetocaloric effect (MCE) has arrested much interest because they could be a promising alternative to supersede costly and scarce helium-3.1-5 And, the quality of magnetic refrigeration can be judged by the magnitude of magnetic entropy change (∆Sm). At the early stage of research on magnetic cooling materials, efforts have been focused on fabricating the 3d molecular clusters (3d refers to magnetic transition metals), such as {Fe8},6 {Fe14},7 {Mn10},8 {Mn12}6 and {Mn14}9 to obtain a large ∆Sm. Nevertheless, the magnetic study indicates that these d-block molecular clusters show small ∆Sm values, which is caused either by a noticeable magnetic anisotropy or a low ground-state spin (S) value.10, 11 Thus, minor anisotropy and large S value are particularly favorable for obtaining large magnetic entropy changes. Considering this, the GdIII ion is an ideal choice to construct magnetic cooling materials owing to its zero orbital magnetic moment and large spin state (S = 7/2). To data, several GdIII-based molecular magnetic cooling materials with large ∆Sm values, for example, {Gd7},12 {Gd10},13 {Gd14},14 {Gd18},15 {Gd24},16 {Gd36},17


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{Gd48},18 {Gd104}19 and {Gd140}20 have been reported. Although these materials possess giant theoretical ∆Sm values, their experimental ∆Sm values calculated from the magnetization data are usually much smaller than the corresponding theoretical ones. It is not surprising since the diamagnetic components in these materials, including organic ligands, free and coordinated solvent molecules, will reduce the magnetic density and hence resulting in a lower experimental ∆Sm values. In order to increase the magnetic density, the relative molecular mass of refrigerant materials should be reduced as much as possible. One approach is to employ appropriate inorganic bridging ligands to substitute the organic ligands. For example, inorganic GdIII materials, such as {GdF3},21 {Gd(OH)3},22 {GdPO4},23 {GdVO4},24 {Gd(OH2)Cl},25 {Gd(OH)CO3},26

{[Gd3(CO3)(OH)6](OH)},27

{Gd4(SO4)4(OH)4(H2O)4},28

{[Gd2(OH)5Cl]·1.5H2O},29 {K3Li3Gd7(BO3)9},30 and {[Gd6O(OH8)(ClO4)4(H2O)6](OH)4},31 have been realized to exhibit impressive MCE properties. Another approach is to assemble polynuclear GdIII-hydroxy clusters as molecular building blocks (MBBs) into high-density metalorganic frameworks (MOFs) with appropriate organic connectors. However, as the hydrolysis of GdIII ion to form GdIII-hydroxy cluster is hard to govern and the presence of rival coordination between the OH– ion and organic ligand, MOFs fabricated by GdIII-hydroxy cluster with significant magnetic entropy changes is still limited.32-34 In this communication, we report two hexanuclear GdIII-hydroxy cluster-based MOFs, namely {H2[Gd6(OH)8(H2O)6(p-BDC-F4)6]·3(2,2′-bpy)·6H2O} (1) and {H2[Gd6(OH)8(H2O)6(m-BDCF4)6]·3(4,4′-bpy)·6H2O} (2) (p-H2BDC-F4 = tetrafluoroterephthalic acid, m-H2BDC-F4 = tetrafluoroisophthalic acid), which are prepared through hydrothermal reactions of GdIII ions with the corresponding dicarboxylic ligands. Single crystal X-ray diffraction (SC-XRD) investigations unveil that they are built from hexanuclear GdIII-hydroxy cluster MBB


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{Gd6(OH)8(COO)12(H2O)6}, but with different topologies. Compound 1 is a 12-connected framework with a face-centered cubic (fcu) topology, whereas 2 is a 6-connected framework with a primitive cubic (pcu) topology. Both of them show stability in some refluxing organic solvents, boiling water, and aqueous solutions at pH = 2−11. Moreover, they exhibit significant −∆Sm values of 28.27 and 29.20 J/Kg·K for 1 and 2, respectively. Reaction of Gd(NO3)3·6H2O, p-H2BDC-F4, and 2,2′-bipyridine in water at 125 °C afforded polyhedral crystals of {H2[Gd6(OH)8(H2O)6(p-BDC-F4)6]·3(2,2′-bpy)·6H2O} (1), in which 2,2′bipyridine is not coordinated to the GdIII ion and instead only acts as a template existing in the channel of the 3D framework. Although 2,2′-bipyridine is not be determined by SC-XRD, their existence can be unequivocally confirmed by elemental analysis and TGA results (Figure S1), as well as by the 1H NMR spectrum, which clearly showed the signals of 2,2′-bipyridine (Figure S2). While similar reactions with m-H2BDC-F4 could not afford any isolable products, using 4,4′-bipyridine as a templating molecule instead of 2,2′-bipyridine allowed the isolation of polyhedral crystals of {H2[Gd6(OH)8(H2O)6(m-BDC-F4)6]·3(4,4′-bpy)·6H2O} (2). The structure analysis of 2, which involves analogous MBB to that of 1, demonstrates that the 4,4′-bipyridine populates all cavities in the structure, interacting with the framework via hydrogen bonding with coordination water molecules on the GdIII cations (O−H···N = 2.719 Å) and – stacking interactions with aromatic rings of the carboxylate ligands (3.482Å). Without the addition of bipyridines, neither 1 nor 2 could be obtained. This suggests their important role as templating molecules which direct the formation of GdIII-carboxylate frameworks around them. Additionally, it should be pointed out that for each compound there must be two protons to balance the negative charge of the network. These protons are most likely attached to some of the pyridine N atoms, generating pyridinium salts as counter cations.


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Compounds 1 and 2 crystallize in cubic system Fm-3m and trigonal system R-3, respectively. In the structure of 1, each GdIII ions displays a nine-coordinated distorted tricapped prismatic geometry (Figure S3), and is coordinated by four μ3-bridging hydroxyl groups, four carboxylate oxygen atoms and one H2O. The neighboring Gd atoms are ligated by two μ3-bridging hydroxyl oxygens and one carboxylate group in a syn-syn mode to give a highly symmetrical hexanuclear MBB {Gd6(OH)8(COO)12(H2O)6} (Figure 1a), where Gd…Gd length is 3.907 Ǻ and Gd−O−Gd angle is 113.61°. For 2, it features a similar {Gd6} MBB, but with different Gd…Gd distances (3.982 and 3.977 Ǻ) and Gd−O−Gd bond angles (113.53 and 114.05°). In 1, each {Gd6} MBB is bridged by 12 p-BDC-F42− anions to form a 3D (Figure S4a), while in 2 it is cross-linked through 6 pairs of m-BDC-F42− anions to generate a 3D framework (Figure S4b). Topologically, {Gd6} MBB can be treated as a node, one p-BDC-F42− anion in 1 (Figure 1b) and one pair of p-BDCF42− anions in 2 (Figure 1c) as connectors. Therefore, the structures of 1 and 2 can be abstracted into the 12-connected fcu and 6-connected pcu networks, respectively (Figures 1d, 1e and S5). Although hexanuclear lanthanide MBBs similar to {Gd6} in 1 and 2 have been shown to form fcu-MOFs with various linear dicarboxylate ligands,35-37 they have never been reported to act as a 6-connected MBB in the construction of pcu-MOFs. Thus, compound 2 is the first example of pcu-MOF fabricated by 6-connected hexanuclear lanthanide MBB. Powder X-ray diffraction (PXRD) data of 1 and 2 are gained at 300 K, and similarities between experimental patterns and simulated ones indicate phase purities of 1 and 2 (Figure S6). Besides, the chemical stability of 1 and 2 are also investigated. The experimental PXRD patterns are aligned with the calculated ones after immersing the prepared samples 1 and 2 in some refluxing organic solvents, for instance methanol, ethanol, dichloromethane, acetonitrile, acetone, N,N-dimethylformamide and boiling water for about 2 h, as well as in water solutions at pH = 2,


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3, 10 and 11 for 24 h, suggesting that the structure integrity was maintained and the phase transition did not occur during the stability testing process (Figure S7). The high chemical stability of 1 and 2 can be attributed to the highly connected metal-containing MBB and the hydrophobic pore surface generated by F atoms. It should be mentioned, however, that in 0.1 M HCl solution (pH = 1), 1 and 2 gradually dissolved (Figure S8), illustrating the collapse of the frameworks. In 0.01 M NaOH solution (pH = 12), the color of 1 and 2 changed in 2 h, and the XRD patterns indicate the phase transition from crystalline to amorphous phases (Figure S9). The xmT versus T curves of 1 and 2 are displayed in Figure 2, which are acquired from 300 to 2 K with H = 0.1 T. The magnetic performance of 1 and 2 is nearly the same, signifying the structure similarity. Thus, only the magnetic property of 1 is described in detail below. The experimental xmT value per {Gd6} unit is 46.65 cm3 mol−1 K at 300 K, this value is slightly low compare to the theoretical value of 47.25 cm3 mol−1 K achieved from six un-coupled GdIII ions. As cooling, xmT products keep practically constant (between 46.65 and 48.20 cm3 mol−1 K) until reaches about 11 K, and then a sharp increase to 50.01 cm3 mol−1 K at lowest temperature is observed (Figure 2a). This low temperature (below 11 K) magnetic behavior undoubtedly suggests the existence of weak intramolecular ferromagnetic (F) coupling in 1. The small positive θ value of 0.9 K, attained through simulating the 1/xm−T data in the whole temperature range using the Curie-Weiss law, can also confirm presence of F interaction (Figure 2a). It is well accepted that the types of super-exchange magnetic interactions (paramagnetic, antiferromagnetic or ferromagnetic) largely depend on the M−O−M bridging angle. Very recently, Tong et al. have demonstrated that the large Gd−O−Gd bond angle (109.96 to 114.29°) commonly mediates the F interaction.38 Therefore, the weak F interactions observed in 1 and 2 should be attributed to the large Gd−O−Gd angles (113.61° for 1, 113.53° and 114.05° for 2).


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Figure 3a and 3c display the magnetization curves (M versus H) of 1 and 2, in which the magnetization for 1 achieves to saturation value 41.56 Nβ (42.19 Nβ for 2) at 2 K and 8 T, very close to 42 Nβ expected for six isolated GdIII ions. Given the large magnetization value and the presence of weak F interaction, the magnetocaloric properties of 1 and 2 were also investigated. Based on the experimental magnetization data, −∆Sm is got using the Maxwell equation and results are presented in Figure 3b (for 1) and 3d (for 2). The calculated −∆Sm values of 1 and 2 modestly rise up as the temperature decreases or the field increases, achieves maximum values of 28.27 and 29.20 J/Kg·K for 1 and 2 (∆H = 8 T at 2 K), respectively. These values are slightly lower than theoretically maximum −∆Sm value (32.58 J/Kg·K for 1 and 2), obtained from 6Rln(2S + 1) (S = 7/2). This disparity should be attributed to the negative contribution of diamagnetic compositions. Nevertheless, they are larger than those reported for some discrete GdIII clusters, such as {Gd2},39 {Gd4},39, 40 {Gd7},12, 41 {Gd12}42 and {Gd18},15 whose −∆Sm values are within the range of 12.93 to 27.7 J/Kg·K. Interestingly, entropy changes for 1 and 2 are still large even in the low field region (15.36 and 15.87 J/Kg·K for 1 and 2, respectively, with ∆H = 2 T). These low field −∆Sm values are larger than commercial applied GGG (Gd3Gd5O12) under the same conditions (about 14.6 J/Kg·K),43,

44

suggesting that 1 and 2 are potential molecule-based

magnetic cooling materials. In summary, with the aid of bipyridine templating molecules, a 12-connected fcu-MOF and a 6-connected pcu-MOF have been successfully fabricated by linking {Gd6(OH)8(COO)12(H2O)6} MBBs through positional isomeric bridging ligands p-BDC-F4 and m-BDC-F4, respectively. Different from the reaction using p-BDC-F4 and 4,4'-bpy, the employment of angular isomer mBDC-F4 and 2,2'-bpy has permitted for the first time the isolation of a pcu-MOF in which the


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hexanuclear GdIII-hydroxy cluster functions as a 6-c pseudo-octahedral MBB. These results demonstrate the isomeric effect of the bridging ligand and the template in the molecular design of metal-organic framework, which allows the tunability for the resulting framework topologies. Due to the high connectivity of the {Gd6} node and the exposed hydrophobic fluorine atoms in channels, compounds 1 and 2 exhibit high robustness in various chemical environments, such as in some refluxing organic solvents, burning H2O and aqueous solutions with pH value of 2−11. Moreover, magnetic investigation shows that 1 and 2 display significant MCE value. These large magnetic entropy changes, especially under low field makes 1 and 2 promising candidates for molecule-based magnetic refrigerants at extreme low temperature. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Materials and characterization, detailed synthesis, X-ray crystallographic data, FT-IR spectra, 1H NMR spectrum, PXRD patterns, TGA curves, and related figures and supplementary tables (PDF) Accession Codes CCDC 1870343 and 1870344 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.au.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. AUTHOR INFORMATION Corresponding Author


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*E-mail: [email protected]; [email protected]. ORCID Shao-Wu Du: 0000-0001-6047-1355 Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This work was supported by the NNSF of China (no. 21571175 and 21503230), NSF of Fujian Province (no. 2018J05032). REFERENCES (1)

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(34) Biswas, S.; Mondal, A. K.; Konar, S., Densely Packed Lanthanide Cubane Based 3D Metal-Organic Frameworks for Efficient Magnetic Refrigeration and Slow Magnetic Relaxation. Inorg. Chem. 2016, 55, 2085‒2090. (35) Xue, D.-X.; Cairns, A. J.; Belmabkhout, Y.; Wojtas, L.; Liu, Y.; Alkordi, M. H.; Eddaoudi, M., Tunable Rare-Earth fcu-MOFs: A Platform for Systematic Enhancement of CO2 Adsorption Energetics and Uptake. J. Am. Chem. Soc. 2013, 135, 7660‒7667. (36) Xue, D.-X.; Belmabkhout, Y.; Shekhah, O.; Jiang, H.; Adil, K.; Cairns, A. J.; Eddaoudi, M., Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction. J. Am. Chem. Soc. 2015, 137, 5034‒5040. (37) Gao, M.-L.; Wang, W.-J.; Liu, L.; Han, Z.-B.; Wei, N.; Cao, X.-M.; Yuan, D.-Q., Microporous Hexanuclear Ln(III) Cluster-Based Metal-Organic Frameworks: Color Tunability for Barcode Application and Selective Removal of Methylene Blue. Inorg. Chem. 2017, 56, 511‒517. (38) Guo, F.-S.; Leng, J.-D.; Liu, J.-L.; Meng, Z.-S.; Tong, M.-L., Polynuclear and Polymeric Gadolinium Acetate Derivatives with Large Magnetocaloric Effect. Inorg. Chem. 2012, 51, 405‒413. (39) Rasamsetty, A.; Das, C.; Carolina Sañudo, E.; Shanmugam, M.; Baskar, V., Effect of coordination geometry on the magnetic properties of a series of Ln2 and Ln4 hydroxo clusters. Dalton Trans. 2018, 47, 1726‒1738.


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(40) Wu, J.; Li, X.-L.; Zhao, L.; Guo, M.; Tang, J., Enhancement of Magnetocaloric Effect through Fixation of Carbon Dioxide: Molecular Assembly from Ln4 to Ln4 Cluster Pairs. Inorg. Chem. 2017, 56, 4104‒4111. (41) Goura, J.; Walsh, J. P. S.; Tuna, F.; Chandrasekhar, V., Synthesis, structure, and magnetism of non-planar heptanuclear lanthanide(III) complexes. Dalton Trans. 2015, 44, 1142‒1149. (42) Zhang, Z.-M.; Zangana, K. H.; Kostopoulos, A. K.; Tong, M.-L.; Winpenny, R. E. P., A pseudo-icosahedral cage {Gd12} based on aminomethylphosphonate. Dalton Trans. 2016, 45, 9041‒9044. (43) Daudin, B.; Lagnier, R.; Salce, B., Thermodynamic Properties of the Gadolinium Gallium Garnet, Gd3Ga5O12, Between 0.05 and 25 K. J. Magn. Magn. Mater. 1982, 27, 315‒322. (44) Slack, G. A.; Oliver, D. W., Thermal Conductivity of Garnets and Phonon Scattering by Rare-Earth Ions. Phys. Rev. B 1971, 4, 592‒609.


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Figure 1. (a) View of the {Gd6(OH)8(COO)12(H2O)6} cluster; (b) Simplified 12-c MBB and the p-BDC-F4 linker in 1; (c) Simplified 6-c MBB and the m-BDC-F4 linker in 2; (c) View of fcu topology of 1; (e) View of pcu topology of 2.


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(a)

(b) Figure 2. The xmT vs T plots and xm‒1 vs T plots for compounds 1 (a) and 2 (b).


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(a)

(b)


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(c)

(d) Figure 3. The M–H plots at temperature range of 2−10 K for 1 (a) and 2 (c); (b) Temperature dependence of –∆Sm values calculated from the magnetization data at the indicated magnetic field change of 1 (b) and 2 (d).


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For Table of Contents Use Only Tuning the Topology from fcu to pcu: Synthesis and Magnetocaloric Effect of MOFs Based on a Hexanuclear Gd(III)-Hydroxy Cluster Wei Wei, †,§ Xue Wang,┴ Kai Zhang, †,§ Chong-Bin Tian,*† and Shao-Wu Du*‡

A 12-connected fcu-MOF and a 6-connected pcu-MOF based on a hexanuclear GdIII-hydroxy cluster MBB are reported. They both exhibit good chemical stability and significant MCE with the −∆Sm value of 28.27 J/Kg·K for 1 and 29.20 J/Kg·K for 2 at 2 K for ∆H = 8 T.


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Tuning the Topology from fcu to pcu: Synthesis and Magnetocaloric

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