Changing the Hydrophobic MOF Pores through Encapsulating

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C: Physical Processes in Nanomaterials and Nanostructures

Changing the Hydrophobic MOF Pores through Encapsulating Fullerene C60 and Metallofullerene Sc3C2@C80 Haibing Meng, Chong Zhao, Mingzhe Nie, Chunru Wang, and Taishan Wang J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b11659 • Publication Date (Web): 22 Feb 2019 Downloaded from http://pubs.acs.org on February 23, 2019

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The Journal of Physical Chemistry

Changing the Hydrophobic MOF Pores through Encapsulating Fullerene C60 and Metallofullerene Sc3C2@C80 Haibing Meng,†‡ Chong Zhao,†‡ Mingzhe Nie,†‡ Chunru Wang*† and Taishan Wang*† †Beijing

National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Molecular

Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun North First Street 2, 100190 Beijing, China. ‡University

of Chinese Academy of Sciences, Beijing 100049, China.

ABSTRACT We report that the encapsulation of fullerene or metallofullerene can greatly change the hydrophobic property of pores for metal-organic frameworks (MOFs). The adsorption capacities for several aromatic molecules (toluene, benzene, xylene, and chlorobenzene) were raised after incorporating C60 into MOF-177. In addition, paramagnetic metallofullerene Sc3C2@C80 with an electron spin was encapsulated into the pores of two kinds of MOFs (MOF177 and MOF-180) filling with toluene solvent. It is found that Sc3C2@C80 electron spin can sense the different pore sizes of MOFs as shown by its varied EPR signals, which are affected by

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the different confinement effect in space. The filling toluene solvent within MOFs plays an important role in steering the spin relaxation of Sc3C2@C80@MOFs through lubricating the motion of Sc3C2@C80 balls. These results revealed that metallofullerene Sc3C2@C80 can act as a spin probe to sensitively detect the pore environment of MOFs. Moreover, the fullerenes and metallofullerenes can act as additives to tune the oleophilic property of MOF pores and it will promote the application of this kind of complex materials as a new adsorbing and separating material.

INTRODUCTION Metal-organic frameworks (MOFs) are constructed from metal clusters/ions (nodes) and organic ligands (linkers).1-5 The intrinsic porosity of MOFs provides a good platform for the incorporation of guests, such as gases, drug molecules, dyes, and fullerenes, resulting in novel complex materials and expanding their properties and applications.4,

6-10

Typically, the

confinement effect of MOF pores can change the chemical or physical properties of guests.11-15 Moreover, the host–guest interaction could stimulate new features of these complex materials.14, 16-20

Fullerene as the only one allotrope of elemental carbon with molecular form has raised great attention since its discovery in 1985.21 Moreover, endohedral metallofullerene Sc3C2@C80 is formed by entrapping Sc3C2 cluster inside C80 fullerene cage.

22-25

The unpaired electron

localized on Sc3C2 cluster couples with three equivalent scandium nuclei, resulting in 22 lines in its electron paramagnetic resonance (EPR) spectrum at room temperature in solution.26-27 Its stable electron spin protected by carbon cage and its magnetic sensitivity endow it with potential


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applications in quantum computing, magnetoreception, spintronics, et al.28-30 In order to promote the applications of Sc3C2@C80, its material design and development is essential. One of the extraordinary characteristics of fullerene C60 and metallofullerene Sc3C2@C80 is their aromatic carbon cages. As spherical molecules, it is fascinating to encapsulate C60 and Sc3C2@C80 into MOF pores and to construct new complex materials with unique properties and applications.11,12 Herein, we report the tunable hydrophobic property of pores for MOFs by means of encapsulating fullerene C60 and metallofullerene Sc3C2@C80. The adsorption capacities for several aromatic molecules were investigated after incorporating C60 into MOF-177. EPR spectroscopy was used to detect the electron spin characters of Sc3C2@C80 within varied pores of MOFs (MOF-177 and MOF-180). Moreover, the toluene effect on Sc3C2@C80 electron spin within MOFs was analyzed. RESULTS AND DISCUSSION The C60 and Sc3C2@C80 was prepared following the Kräschmer–Huffman arc-discharge method and isolated by high performance liquid chromatography (HPLC).23,

26

MOF-177 and

MOF-180 were synthesized according to the literature method.1 Then the crystals were soaked and washed with toluene for more than three times to remove other solvents from the pores. The C60@MOF-177 was prepared according to literature method.10 Briefly, 5 mg as-prepared MOF177 was kept in 1.0 ml of toluene solution of C60 (0.05 mg) at room temperature for a week. The obtained C60@MOF-177 was washed with fresh toluene for several times and then dried completely in vacuum drying oven. The aromatic frameworks and pores of MOF-177 (larger than 10.8 Å) and MOF-180 (larger than 15.0 Å) provide suitable space for accommodating larger Sc3C2@C80 (the diameter is about 8 Å). Therefore, Sc3C2@C80 can be well incorporated into the


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pores of above two MOFs. Experimentally, the as-prepared MOF-177 and MOF-180 (5.0 mg) were placed into 1.0 ml of toluene solution of Sc3C2@C80 (0.15 mg) for a week to assure the adequate incorporation of Sc3C2@C80 (Figure 1). The obtained sample was washed with fresh toluene for several times and the surface was dried with nitrogen gas for further measurements. In order to investigate the toluene effect on Sc3C2@C80, the obtained complex powders were not further dried in vacuum drying oven.

Figure

1.

Schematic

representations

of

MOF

and

toluene-filled

C60@MOF

and

Sc3C2@C80@MOF. The pores of MOF can be occupied by Sc3C2@C80 or C60 molecules, which are represented by the light gray sphere. The carbon atoms of Sc3C2@C80 or C60 cages are colored in dark gray sphere and the scandium atoms are colored in red sphere. The internal carbon atoms in Sc3C2@C80 are highlighted by blue color. Toluene molecules are colored in yellow sphere. The organic ligands are colored in orange and the metallic nodes are highlighted in green color. In order to investigate the adsorption capacity, we performed the adsorption isotherms of several aromatic solvents for solvent-free MOF-177 and C60@MOF-177, as shown in Figure 2b


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and Table 1. Obviously, the incorporation of C60 can greatly enhance the absorbability of MOF177 for aromatic organic molecules, which does not disrupt the crystal structure of MOF-177 (Figure 2a). To be specific, the toluene adsorption capacities for MOF-177 and C60@MOF-177 are 361.15 mg/g and 798.34 mg/g, respectively. Moreover, the adsorption capacities for other aromatic solvents (benzene, xylene, and chlorobenzene) were also greatly improved after incorporating C60 into MOF-177. In addition, we performed the acetone adsorption isotherms of dried MOF-177 and C60@MOF-177 at 298 K for comparison (Figure S3). However, the uptake of acetone is reduced after MOF-177 accommodates C60. These results reveal that the encapsulation of fullerene can change the hydrophobic property of pores for MOFs and typically enhance the absorbability of MOF for aromatic organic molecules. For several reports, the effect of polarity and hydrophilicity/hydrophobicity of organics on adsorption capacities of MOFs have been discussed, for which the MOFs with organic frameworks have advantages to absorb organics and even oil.31-33 Herein, the encapsulated aromatic fullerene could greatly increase the oleophilic surface of MOF-177 pores. Consequently, more aromatic molecules can be adsorbed by C60@MOF-177 through π–π interaction. As shown in Figure 2c, the PXRD patterns of toluene-filled MOF-177 and toluene-filled Sc3C2@C80@MOF-177 are similar, which indicates that the accommodation of Sc3C2@C80 doesn't disrupt the crystal structure of MOF-177. Similarly, the characteristic PXRD peaks of toluene-filled Sc3C2@C80@MOF-180 don't exhibit big changes as well (Figure 2d). To verify the structure of MOF-180, we also made a PXRD comparison of the as-prepared MOF-180 and toluene-filled MOF-180 (Figure S2). The PXRD pattern of as-prepared MOF-180 is in agreement with the reported and simulated patterns of MOF-180.1 After toluene was filled, the resulted PXRD pattern changed and some fine peaks became broadened caused by the induced


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toluene, showing some defects of toluene-filled MOF-180 crystals. Even so, the main peaks were maintained in toluene-filled MOF-180, revealing its unchanged whole crystalline network. Moreover, the transmission electron microscopy (TEM) elements mapping illustrated the dispersed scandium element stemmed from Sc3C2@C80, demonstrating the incorporation of Sc3C2@C80 within MOFs (Figure S1).13

Figure 2. (a) PXRD patterns of dried MOF-177 (black curve) and dried C60@MOF-177 (red curve). (b) Toluene adsorption isotherms of dried MOF-177 (black curve) and C60@MOF-177 (red curve). (c) PXRD patterns of toluene-filled MOF-177 (black curve) and toluene-filled Sc3C2@C80@MOF-177 (red curve). The insets show the optical images of toluene-filled MOF177 (left) and toluene-filled Sc3C2@C80@MOF-177 (right) (d) PXRD patterns of toluene -filled MOF-180 (black curve) and toluene-filled Sc3C2@C80@MOF-180 (red curve). The insets show


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the optical images of toluene-filled MOF-180 (left) and toluene-filled Sc3C2@C80@MOF-180 (right). The paramagnetic properties of metallofullerene Sc3C2@C80 within the pores of two kinds of MOFs (MOF-177 and MOF-180) filling with toluene solvent were then studied by EPR spectrometer. We performed continuous-wave EPR measurements on the toluene-filled Sc3C2@C80@MOFs at 293 K (Figure 3). Obviously, the encapsulated Sc3C2@C80 within different MOFs exhibits different EPR signals, revealing the spin relaxation and isotropy of Sc3C2@C80 were disrupted due to the confinement effect in MOF space. Table 1. The absorption capacity (mg•g-1) of dried MOF-177 and C60@MOF-177 for aromatic molecules. Aromatic molecules

MOF-177

C60@MOF-177

Toluene

361.15

798.34

Benzene

157.90

797.50

Xylene

99.34

786.19

Chlorobenzene

115.23

1002.57

The EPR spectrum of toluene-filled Sc3C2@C80@MOF-177 complex is different from that of pristine Sc3C2@C80 in toluene solution as well as solvent-free Sc3C2@C80@MOF-177 at 293 K.13 The EPR spectrum of Sc3C2@C80 in toluene shows 22 lines (aSc = 6.28 G × 3). But the EPR spectrum of solvent-free Sc3C2@C80@MOF-177 at 293 K exhibits different shape (a1 = 6.00 G, a2 = 6.10 G, a3 = 6.21 G), caused by strong π–π interaction between Sc3C2@C80 and MOF. The EPR spectrum of toluene-filled Sc3C2@C80@MOF-177 at 293 K showed clearly different EPR


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parameters (a1 = 6.28 G, a2 = 6.24 G, a3 = 6.21 G), which exhibit similar EPR pattern with that of Sc3C2@C80 in toluene. Moreover, the toluene-filled Sc3C2@C80@MOF-180 shows more similar pattern (a1 = 6.26 G, a2 = 6.24 G, a3 = 6.23 G) with that of Sc3C2@C80 in toluene solution (Figure S6).

Figure 3. The cage-like structures of MOF-177 (a) and MOF-180 (c) in single pore of them. The green spheres are placed in the structure for clarity and to indicate space in the cage. Zn, blue; O, red; and C, black. H atoms and other molecules are omitted. The EPR spectra of Sc3C2@C80 in toluene-filled MOF-177 (b) and MOF-180 (d) at 293 K.


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Figure 4. Temperature-dependent EPR spectra of Sc3C2@C80 in toluene-filled MOF-177 (a) and MOF-180 (d). Temperature-dependent EPR peaks intensity of Sc3C2@C80 in toluene-filled MOF-177 (b) and MOF-180 (e). Temperature-dependent line width of the EPR spectra for Sc3C2@C80 in toluene-filled MOF-177 (c) and MOF-180 (f). To further exploit the electron spin properties of Sc3C2@C80 in toluene-filled MOFs, the temperature-dependent EPR studies were performed, as shown in Figure 4. For toluene-filled Sc3C2@C80@MOF-177 and Sc3C2@C80@MOF-180, the results revealed that the EPR peak intensity (the peak to peak height at MI = 1/2 (central part of the EPR spectra)) is gradually increased when decreasing temperature from 293 to 193 K (Figure 4a, 4b, 4d and 4e). Accordingly, the line width analyses at MI = 1/2 were performed to illustrate the changes of EPR signals and the results showed a decreasing trend in EPR line widths under low temperature due to the decreased spin-lattice interaction (Figure 4c and 4f). These results are similar to those of Sc3C2@C80 in toluene solution. It can be further illustrated by the identical line width of EPR


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spectra for toluene-filled Sc3C2@C80@MOF plotted against quantum number MI of the Sc3 nuclear magnetic moment at 293 K (Figure 5 and S4). However, for solvent-free Sc3C2@C80@MOF-177, its EPR peak intensity is straightly reduced when decreasing temperature from 293 to 193 K, caused by strong π–π interaction between Sc3C2@C80 and MOF. That is because in solvent-free MOF, the motion of Sc3C2@C80 is restricted by the host–guest interaction inside the frameworks. When the temperature is decreased, the motion of Sc3C2@C80 is further suppressed due to the contraction of MOF pore. Notably, the vast toluene around Sc3C2@C80 in toluene-filled MOF-177 and MOF-180 can weaken the strong interaction from the frameworks and lubricate the motion of Sc3C2@C80. We then analyzed the EPR spectra of toluene-filled Sc3C2@C80@MOF-177 in detail (Figure 5a and 5b). In addition, we performed the spin-lattice relaxation time (T1) measurements on toluene-filled Sc3C2@C80@MOF-177 (Figure 5c) and Sc3C2@C80 solution (Figure 5d) for comparison. For Sc3C2@C80 in solvent-free MOF-177, the restricted motion is resulted from the strong host–guest interaction, leading to the anisotropic hyperfine couplings of Sc3C2@C80. For Sc3C2@C80 in toluene-filled MOF-177, the anisotropic hyperfine couplings of Sc3C2@C80 still can be seen (Figure 5a), but the line widths at different quantum number MI of the Sc3 nuclear magnetic moment do not change (Figure 5b). These results reveal that the toluene solvent around Sc3C2@C80 can lubricate its motion within the pores of MOF-177 and then modulate the spin relaxation of Sc3C2@C80. As a result, the motion of Sc3C2@C80 in toluene-filled MOF-177 is less restricted but not free, which resulted in the slightly inequivalent scandium nuclei.


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Figure 5. (a) Experimental (black) and simulated (red) EPR spectra of toluene-filled Sc3C2@C80@MOF-177. (b) Line width of the EPR spectra for toluene-filled Sc3C2@C80@MOF177 plotted against quantum number MI of the Sc3 nuclear magnetic moment at 293 K. (c) Normalized temperature-dependent T1 of toluene-filled Sc3C2@C80@MOF-177. (d) Normalized temperature-dependent T1 of Sc3C2@C80 in toluene.

Theoretically, according to Kivelson's theory 34, the line width of the peak-to-peak △ 𝐻𝑝𝑝 for Sc3C2@C80 depends on the quantum number (𝑚𝐼) in the EPR spectra and can be expressed as the form △ 𝐻𝑝𝑝 = k0 + k1𝑚𝐼 + k2m2𝐼 + k4𝑚4𝐼


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where all the 𝑘𝑖 parameters depend on the rotational correlation time 𝜏𝑐(𝜏𝑐 = 4𝜋𝜂𝑅3/3𝑘𝑇), which is originated from the Debye theory of rotational relaxation 24, 35. In this formula, η is the viscosity of the solvent and R is the hydrodynamic radius of the molecule. For Sc3C2@C80 in solvent-free MOF-177, △ 𝐻𝑝𝑝 is dependent on 𝑚𝐼, leading to partial disappearance of side EPR signals and exhibiting the anisotropic hyperfine couplings. But for Sc3C2@C80 in toluene-filled MOF-177, △ 𝐻𝑝𝑝 is independent on 𝑚𝐼, which can be clearly seen from the Figure 5b. Therefore, △ 𝐻𝑝𝑝 of Sc3C2@C80 in toluene-filled MOF-177 is directly determined by 𝑘0, which can be expressed as the form 35 𝑘0 = π 𝜏𝑐{(7/45)(Δγ𝐵0)2 + 63𝑏2/16} + K where Δγ and 𝑏 are related with the anisotropic magnitudes of g factors and hyperfine coupling constants. K is related with the anisotropies of g factors. Obviously, the line width of Sc3C2@C80 in toluene-filled MOF-177 is determined by both the viscosity of toluene and the host–guest interaction from the frameworks. The special interaction between Sc3C2@C80 and MOF-177 lubricated by toluene also can be reflected by the spin relaxation time of Sc3C2@C80. The spin-lattice relaxation time T1 can be obtained by measuring EPR continuous wave (CW) power saturation curve of it,36 the details have been illustrated in S7. With decreasing temperature, the toluene-filled Sc3C2@C80@MOF177 shows elongated spin-lattice relaxation time (T1), and this trend is similar with that of Sc3C2@C80 in toluene. As at low temperature, the spin-lattice interaction for Sc3C2@C80 in toluene-filled MOF-177 is weakened, leading to the enhanced T1. However, for toluene-filled Sc3C2@C80@MOF-177, the shortened T1 at T < 213 K shows that the host–guest interaction


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between Sc3C2@C80 and MOF-177 still exists, which would intensify the spin-lattice interaction at lower temperature. CONCLUSIONS In summary, the encapsulation of fullerene or metallofullerene can greatly change the hydrophobic property of MOF pores. The adsorption capacities for aromatic solvents were raised after incorporating C60 into MOF-177. The paramagnetic metallofullerene Sc3C2@C80 was also introduced into the pores of toluene-filled MOF-177 and MOF-180. As shown by the varied EPR signals, the Sc3C2@C80 electron spin can sense the different pore sizes of two MOFs through different host–guest interactions. In addition, the filling toluene solvent plays an important role in steering the spin relaxation of Sc3C2@C80 within two MOFs through lubricating the motion of Sc3C2@C80. These results revealed that metallofullerene Sc3C2@C80 can act as a spin probe to detect the pore size and environment of MOFs sensitively. These findings also offer an effective method to control the magnetic properties of metallofullerenes by altering the pore environment of MOFs, which would help to construct more functional materials. Moreover, the fullerenes and metallofullerenes can act as additives to tune the oleophilic property of MOF pores, and it will promote the application of this kind of complex materials. ASSOCIATED CONTENT Supporting Information. Materials, Synthesis, PXRD data and other characterizations. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author


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*E-mail: [email protected]; [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (61227902, 51672281, 51832008). T. Wang particularly thanks the Youth Innovation Promotion Association of CAS (2015025). REFERENCES 1. Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. Ö.; Snurr, R. Q.; O'Keeffe, M.; Kim, J., et al., Ultrahigh Porosity in Metal-Organic Frameworks. Science 2010, 329, 424. 2. Zhou, H.-C.; Long, J. R.; Yaghi, O. M., Introduction to Metal-organic Frameworks. Chem. Rev. 2012, 112, 673-674. 3. Zhu, Q.-L.; Xu, Q., Metal-organic Framework Composites. Chem. Soc. Rev. 2014, 43, 54685512. 4. Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M., The Chemistry and Applications of Metal-Organic Frameworks. Science 2013, 341. 5. Xiaobin X.; Yan L.; Yong Y.; Farhat N.; Xun W., Tuning the Growth of Metal-Organic Framework Nanocrystals by Using Polyoxometalates as Coordination Modulators. Sci. China Mater. 2015, 58, 370. 6. Cui, Y.; Li, B.; He, H.; Zhou, W.; Chen, B.; Qian, G., Metal-organic Frameworks as Platforms for Functional Materials. Acc. Chem. Res. 2016, 49, 483-493. 7. Tanabe, K. K.; Cohen, S. M., Postsynthetic Modification of Metal-organic Frameworks-a Progress Report. Chem. Soc. Rev. 2011, 40, 498-519. 8. Férey, G.; Serre, C., Large Breathing Effects in Three-Dimensional Porous Hybrid Matter: Facts, Analyses, Rules and Consequences. Chem. Soc. Rev. 2009, 38, 1380-1399. 9. Wenchang, Y.; Cheng-an, T.; Fang, W.; Jian, H.; Tianliang, Q.; Jianfang, W., Tuning Optical Properties of MoF-Based Thin Films by Changing the Ligands of Mofs. Sci. China Mate. 2018, 61, 391. 10. Chae, H. K.; Siberio-Pérez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O'Keeffe, M.; Yaghi, O. M., A Route to High Surface Area, Porosity and Inclusion of Large Molecules in Crystals. Nature 2004, 427, 523. 11. Li, Y.; Wang, T.; Meng, H.; Zhao, C.; Nie, M.; Jiang, L.; Wang, C., Controlling the Magnetic Properties of Dysprosium Metallofullerene within Metal-organic Frameworks. Dalton Trans. 2016, 45, 19226-19229.


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Changing the Hydrophobic MOF Pores through Encapsulating

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