Comparative Stability and Sorption Study of Two the-type Metal

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Comparative Stability and Sorption Study of Two the-type MOFs with Different Multiplicate Metal-Ligand Interactions in SBUs Guoliang Liu, Bei-Bei Li, Yan-Xi Tan, Kongzhao Su, and Daqiang Yuan Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01716 • Publication Date (Web): 11 Jan 2017 Downloaded from http://pubs.acs.org on January 13, 2017

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Crystal Growth & Design

Comparative Stability and Sorption Study of Two the-type MOFs with Different Multiplicate MetalLigand Interactions in SBUs Guoliang Liu ‡,a Bei-Bei Li,‡,a,b Yan-Xi Tan,*,a Kongzhao Sua and Daqiang Yuan*,a a

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

Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China. bUniversity of the Chinese Academy of Sciences, Beijing, 100049, China.

ABSTRACT By regulating secondary building units and inducing multiplicate metal-ligand interactions, an unstable anionic framework MOF-Mn4Cl is structurally modified into a robust neutral framework MOF-Mn4. Althought possessing same network topology, MOF-Mn4 shows a high BET surface area of 1718 m2/g, which is about an 8 times enhancement over MOF-Mn4Cl.

Design and fabrication of metal–organic frameworks (MOFs) have attracted increasing interest due to their aesthetic structural topologies and potential applications in gas adsorption and storage,1, 2 catalyst supports,3, 4 electrode materials,5, 6 chemical sensing,7, 8 controlled release of drugs,9 and light harvesting.10, 11 However, almost all of the applications, especially gas sorption

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performance, are highly depended on the permanent porosity of MOFs.12,

13

Except for

conventional solvent-exchange and heat-treatment,14-16 some special activated methods, such as supercritical carbon dioxide exchange17 and freeze-drying,18, 19 have been used to maintain the structural integrity of MOFs. Compared to above physically activated method, chemical processes (including post-synthetic metathesis and oxidation (PSMO),20 self-interpenetration,21-23 inserting rigid pillar ligand,24, 25 etc.) can more fundamentally optimize the stability of the MOFs, owing to the change of metal-donor affinity and linkage. For example, Zhang’s groups provided a strategy of inserting rigid pillar ligand to structurally modify an unstable lvt-type framework into a rigid seh-type framework.24 Utilizing PSMO strategy, Zhou and co-workers obtained robust PCN-426-Fe(III) and PCN-426-Cr(III) from unstable PCN-426-Mg via stepwise single– crystal-to-single-crystal

transformation.20

However,

these

transformations

are

usually

accompanied by the change of metal nodes and/or topologies of the frameworks. Here, we provide a new idea for enhancing MOFs’ stability via regulating coordination environment of secondary building units (SBUs), including extracting central atoms and changing coordinated mode of ligands. These adjustments will promote formation of some additional interactions between donors and metals, while metal nodes and topologies of the original frameworks are still kept, which is very important for some special applications for MOFs, such as fluorescence, biological monitoring as well as gas sorption/separation. The pores with slightly different environment in MOFs are a better platform to detailedly study the effect of environment on gas sorption properties.26-29 However, few researches reported on this topic. In this work, we report the synthesis, structural characterizations and sorption properties of two new MOFs based on a triangle BTTC3- ligands (H3BTTC = benzo-(1,2;3,4;5,6)-tris(thiophene2’-carboxylic acid) ligand, namely [H2NMe2]3n·[(Mn4Cl)3(BTTC)8(H2O)12]2n (MOF-Mn4Cl) and


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[(Mn4)3(BTTC)8(H2O)12]n·[Mn(OH)2(H2O)4]n (MOF-Mn4), which are consisted of chloridecentered square-planar [Mn4(µ4-Cl)(COO)8]- and [Mn4(COO)8] units linked by the BTTC ligands, respectively. Althought the two MOFs have similar the-type networks formed by the close packing of octahedral and cuboctahedral cages, the framework of MOF-Mn4Cl tends to collapse after the removal of solvent molecules and shows very low gas uptakes. However, once regulating the coordination environment of SBUs in this similar framework, the resulting MOFMn4 is very robust and exhibits a high BET surface area of 1718 m2/g, which is about 8 times enhancement over the unstable anionic MOF-Mn4Cl. Solvothermal reaction of H3BTTC with MnCl2·2H2O in mixture of DMA, MeOH, and aqueous HNO3 (65%) (DMA = N,N’-dimethylacetamide, MeOH = methanol) afforded the cubic crystals of MOF-Mn4Cl. Single crystal diffraction analysis reveals that MOF-Mn4Cl crystallizes in the cubic space group Pm3ത m and consists of chloride-centered square-planar [Mn4(µ4-Cl)(COO)8]- SBUs and triangle BTTC3- ligands with syn-syn carboxylic coordination mode (Figure 1a). As shown in Figure 1b, each Mn(II) adopts a six coordinated octahedral geometry completed by four O atoms from different carboxyl groups of BTTC3- ligand, one µ4Cl center and one terminal H2O molecule.


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Figure 1 Crystal structures of MOF-Mn4Cl and MOF-Mn4. a) The coordination environment of [Mn4(µ4-Cl)(COO)8]- SBU and BTTC ligand in MOF-Mn4Cl (Gray: C; Red: O; Yellow: S; Violet: Mn; Lime: Cl). b) The truncated octahedral cage in MOF-Mn4Cl. c) The cuboctahedral


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cage in MOF-Mn4Cl. d) The cubic packing of octahedral and cuboctahedral cages via sharing all of the triangular facets in both MOFs. e) The diagram of the 3D framework of MOF-Mn4Cl. f) The coordination environment of [Mn4(COO)8]- SBU and BTTC ligand in MOF-Mn4. g) The truncated octahedral cage in MOF-Mn4, in which [Mn(OH)2(H2O)4] unit is wrapped. h) The cuboctahedral cage in MOF-Mn4. i) 3,8-Connected the topology derived from the structure of both MOFs. j) The diagram of the 3D framework of MOF-Mn4. And then each Mn(II) shares one µ4-Cl and two carboxylates with adjacent Mn(II), forming a chloride-centered square-planar [Mn4(µ4-Cl)(COO)8]- SBU with D4h symmetry. It is worth noting that the bond length (2.826 Å) of Mn-Cl bond is longer than that (2.625 Å) of previous reported [Mn4(µ4-Cl)(COO)8]- unit and other similar inorganic M4Cl units.30, 31 In the structure, each [Mn4(µ4-Cl)(COO)8]- SBU is surrounded by eight BTTC3- ligands, while each BTTC3ligand links three [Mn4(µ4-Cl)(COO)8]- SBUs. Moreover, there are two kinds of open cages in the whole framework. One is a octahedral cage with a diameter of about 2.1 nm (Mn···Mn distance), which is formed by six [Mn4(µ4-Cl)(COO)8]- squares as vertexes and eight BTTC3ligands (Figure 1b). All of the triangular facets on the octahedral cage are covered by BTTC3ligands. Another is a cuboctahedral cage with a diameter of about 2.6 nm (Mn···Mn distance), which is constituted by twelve [Mn4(µ4-Cl)(COO)8]- squares as vertexes and eight BTTC3ligands (Figure 1c). In the cuboctaheral cages, eight triangular facets are shared with the octahedral cage and also covered by BTTC3- ligands, while six square facets are all opening. The close packing of these octahedral and cuboctahedral cages via sharing all of the triangular facets further extends the structure into a 3D open framework (Figure 1d and 1e). Within these large octahedral and cuboctahedral cages, the framework possesses considerable void space, and the solvent accessible volume is estimated by PLATON to be about 67% of the total crystal volume.


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The cuboctaheral cages are interconnected, thereby forming 3D open channels with an aperture diameter of 2 nm; these channels are filled with disorder solvent molecules and balanced cations. From the topological point of view, the [Mn4(µ4-Cl)(COO)8]- squares and BTTC3- ligands can be regarded as 8- and 3-connecting nodes, respectively. Hence, the final framework is simplified into a (3,8)-connected the network (Figure 1i), which has been known in several reported MOFs based on the similar inorganic M4Cl (or M4O) units connected by 1,3,5-benzenetricarboxylate, 4,4’,4’’-s-triazine-2,4,6-triyltribenzoic

acid,

triphenylene-2,6,10-tricarboxylate,

5,5’,10,10’,15,15’-hexameth-yltruxene-2,7,12-tricarboxyllate or 1,3,5-tris(tetrazol-5-yl)benzene ligands.32-36 These MOFs were all stable for gas sorption upon activation or ion-exchange. Cubic crystals of MOF-Mn4 can be successfully obtained by the reaction condition of MOFMn4Cl except that aqueous HNO3 was replaced by acetic acid. Single crystal diffraction analysis reveals that MOF-Mn4 crystallizes in the cubic space group Fm 3ത c, which is expectedly constructed by square-planar tetranuclear manganese units linked by triangle BTTC3- ligands. Notebly, the syn-anti carboxylic coordination mode of each BTTC3- ligand is different to that in MOF-Mn4Cl (Figure 1f). In the structure of MOF-Mn4, each Mn(II) adopts a five coordinated square-pyramidal geometry, which is coordinated by four O atoms from four different BTTC3ligands and one O atom from terminal water molecular. Each Mn(II) is bridged to each of two other neighbouring Mn(II) through two carboxyl group via syn-trans configuration, forming a square [Mn4(COO)8] SBU. Additionally, a weak coordination interaction between O3 and Mn1 (Mn···O = 2.637 Å) can be observed (Figure 1f). Consequently, the symmetry of the [Mn4(COO)8] SBU reduces to C4h owing to the change of coordination mode of BTTC3- ligands. Although some structural details are different from MOF-Mn4Cl, MOF-Mn4 also owns octahedral and cuboctahedral cages consisted of the linkage of [Mn4(COO)8] SBUs and BTTC3-


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ligands (Figure 1g and 1h). The close packing of these octahedral and cuboctahedral cages are also similar to that of MOF-Mn4Cl, resulting in the 3D framework of MOF-Mn4 with the topology (Figure 1d, 1i and 1j). Interesting, there is an isolated [Mn(OH)2(H2O)4] unit inside each twisted octahedral cage (Figure 1g). The solvent accessible volume of MOF-Mn4 is about 62.5% of the total crystal volume, which is slight lower than that of MOF-Mn4Cl. Thus, it can be considered as successful tuning of coordination environment of SBUs in MOF-Mn4Cl. Meanwhile, the original anionic framework is turned into a neutral one. In the previous work, Zhou’s group presented a neutral meso-MOF-2, which was constructed by connecting squareplanar tetranuclear Cd(II) SBUs with BTTC3- ligands, and retained permanent porosity upon heating activation.37 MOF-Mn4 is isostructural with meso-MOF-2 because of the presence of square-planar tetranuclear Mn(II) unit which has not been reported so far. It encourages us to explore the gas sorption property of MOF-Mn4.

Figure 2 The XRPD patterns of simulated one of MOF-Mn4Cl (a), as-synthesized MOF-Mn4Cl (b), MOF-Mn4Cla (c), simulated one of MOF-Mn4 (d), as-synthesized MOF-Mn4 (e), MOFMn4a (f), MOF-Mn4c (g), MOF-Mn4d (h).


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X-ray powder diffraction (XRPD) measurement confirmed the phase purity of MOF-Mn4Cl (Figure 2a and 2b). To examine the stability of MOF-Mn4Cl, thermal gravimetric analysis (TGA) and desolvation experiment are carried out. The TGA results show that MOF-Mn4Cl releases guest molecules between 25 and 250 oC, leading to a weight loss of 31% (Figure S1.). To completely remove guest molecules in the voids by degassing, solvent exchange is performed by soaking crystals of MOF-Mn4Cl in CH2Cl2 under ambient conditions for 24 hour, and then the CH2Cl2-exchanged sample is degassed under high vacuum (5 µmHg) at room temperature overnight to form desolvated solid MOF-Mn4Cla. XRPD pattern of desolvated solid MOFMn4Cla is distinct from that of original MOF-Mn4Cl, confirming the host framework appears to undergo significant pore collapse upon guest removal (Figure 2c). This phenomenon was often seen in some high porous MOFs.38-41 The TGA curve of MOF-Mn4 shows that the guest molecules escape at a higher temperature (Figure S1). So, CH2Cl2-exchange is also performed for crystals of MOF-Mn4, which is further degassed under high vacuum (5 µmHg) at room temperature overnight to give the desolvated solid MOF-Mn4a, whose XRPD pattern is matched well with that of original MOF-Mn4, confirming the integrity of the framework upon guest removal (Figure 2c-e). In order to deeply understand the thermostability of host framework, MOF-Mn4 is also degassed under 220, 250 and 280 oC, giving MOF-Mn4b, MOF-Mn4c and MOF-Mn4d, respectively. XRPD patterns results indicate that the host framework of MOF-Mn4 is stable under 250 oC and high vacuum. It is noted that high porous MOFs with such excellent thermostability are rarely reported. Once the activated temperature rise to 280 oC, the collapse of most host framework can be verified by XRPD pattern and gas sorption shown as below.


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Figure 3 N2 Gas sorption isotherms at 77 K: a) MOF-Mn4Cla; b) MOF-Mn4a; c) MOF-Mn4b; d) MOF-Mn4c; e) MOF-Mn4d. Since both of MOF-Mn4Cl and MOF-Mn4 possess similar porous structure and same topology, it provides a platform to comparatively study that how slight structural changes influence gas sorption performance. The N2 sorption isotherms reveals that MOF-Mn4Cla has a very low N2 uptake of 64.5 cm3/g at 77 K and 1 bar, giving low Langmuir and BET surface areas of 225 and 194 m2/g, respectively (Figure 3a). The surface area and porosity parameters of the ─d are also analysed by standard N2 analysis at 77 K. As shown in activated sample MOF-Mn4a─ Figure 3b-3e, the all of samples displaye a Type I isotherm with a steep nitrogen gas uptake at low relative pressure (P < 0.1 bar), indicating permanent microporosity of the framework. The BET surface area for MOF-Mn4a is calculated to be 1282 m2/g. In a series of the activated sample, MOF-Mn4c shows the highest gas uptake of 427.6 cm3/g and BET surface areas of 1718 m2/g, which are about 8 times enhancement over those of the anionic MOF-Mn4Cl and comparable to MOFs that based on square-planer M4X (M = metal ions, X = Cl、O or not exist)


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SBUs (Table S2). Being different from the isostructural meso-MOF-2, MOF-Mn4d shows much higher N2 uptake than meso-MOF-2 and no terthienobenzene loss can be observed in MOFMn4c, further affirming its excellent thermostability. The experimental total pore volume of MOF-Mn4c is 0.66 cm3/g, which is slightly lower than that (0.76 cm3/g) estimated from the single crystal structure without all dissociative and coordinated solvent molecules. For MOFMn4a ─ c, the pore size distribution evaluated from a non-local density functional theory (NLDFT) simulation of the N2 sorption curve indicated that the average pore size increases with the increasing of activated temperature. (Figure S2). Under 77 K and 800 mmHg, the H2 capacity of MOF-Mn4a is 109 cm3/g (0.97 wt%), which can compared with those of many reported MOFs.42, 43 (Figure S3). The enthalpy of H2 adsorption for MOF-Mn4a is estimated from the H2 sorption isotherms at 77 and 87 K by using the virial equation to understand the affinity of MOF-Mn4a toward H2, giving an isosteric heat of 5.3 kJ/mol (Figure S4). The different adsorption properties of MOF-Mn4 and MOF-Mn4Cl are mainly caused by the change of coordination environment in SBUs. MOF-Mn4 and MOF-Mn4Cl have similar porous structure and same topology, but the Mn-Cl bond with long bond length in MOF-Mn4Cl are apt to break during solvent-exchange and degassing processes, causing significant pore collapse in host framework. While each Mn-Cl bond is substituted by two weak coordination interactions of Mn1···O3 in MOF-Mn4, the multiplicate metal-ligand affinity contributes to keep the integrity of the framework upon guest removal. However, such weak interactions can’t be observed in MOF-Mn4Cl because of the long distance of 3.635 Å between Mn and O atoms. In conclusion, by varying coordination environment in SBUs, two Mn(II)-BTTC frameworks with the topology are all successfully synthesized, which are constructed by the close packing of octahedral and cuboctaheral cages. It is interesting that the slight change of coordination


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environment in SBUs make a huge difference in framework stability and gas sorption property between the two Mn(II)-BTTC MOFs. The results reveal that the multiplicate metal-ligand interactions would be benefit for enhancing the MOFs’ stability. ASSOCIATED CONTENT Supporting Information. Experimental procedures, supplementary figures and tables. 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. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT The work was supported by the NSFC (21390392, 21603229), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), and the Nature Science Foundation of Fujian Province (2016J01080, 2016J05056). REFERENCES (1) Li, J. R.; Sculley, J.; Zhou, H. C., Chem. Rev. 2012, 112, 869-932.


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Based on the idea of regulating coordination environment of SBUs in MOFs via inducing multiplicate metal-ligand interactions, an unstable framework MOF-Mn4Cl is structurally modified into a robust framework MOF-Mn4. Although both MOFs possess similar the-type topologies and pore features, the neutral stable MOF-Mn4 shows a high BET surface area of 1718 m2/g, which is about an 8 times enhancement over the unstable anionic MOF-Mn4Cl.


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Comparative Stability and Sorption Study of Two the-type Metal

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