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Enhancing Pore-Environment Complexity using A Trapezoidal Linker: Towards Stepwise Assembly of Multivariate Quinary MOFs Jiandong Pang, Shuai Yuan, Junsheng Qin, Mingyan Wu, Christina T. Lollar, Jialuo Li, Ning Huang, Bao Li, Peng Zhang, and Hong-Cai Zhou J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b07411 • Publication Date (Web): 19 Sep 2018 Downloaded from http://pubs.acs.org on September 19, 2018

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Journal of the American Chemical Society

Enhancing Pore-Environment Complexity Using A Trapezoidal Linker: Towards Stepwise Assembly of Multivariate Quinary MOFs Jiandong Pang,†,‡ Shuai Yuan,*,† Junsheng Qin,† Mingyan Wu,‡ Christina T. Lollar,† Jialuo Li,† Ning Huang,† Bao Li,† Peng Zhang,† and Hong-Cai Zhou*,† †

Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China Supporting Information Placeholder

‡

ABSTRACT: Multi-component metal–organic frameworks (MOFs) promise the precise placement of synergistic functional groups with atomic-level precision, capable of promoting fascinating developments in basic sciences and applications. However, the complexity of multi-component systems has posed a challenge in their structural design and synthesis. Herein, we show that linkers of low symmetry can bring new opportunities to the construction of multi-component MOFs. A carbazoletetracarboxylate linker of Cs point group symmetry was designed and combined with an 8-connected Zr6 cluster to generate a lowsymmetry MOF, PCN-609. PCN-609 contains coordinatively unsaturated Zr sites arranged within a lattice with three crystallographically distinct pockets, which can accommodate linear linkers with different lengths. Sequential linker installation was carried out to postsynthetically insert three linear linkers into PCN-609, giving rise to a quinary MOF. Functionalization of each linker from the quinary MOF system creates multivariate pore environments with unprecedented complexity.

Metal–organic frameworks (MOFs), also known as porous coordination polymers (PCPs), are a class of porous materials constructed by linking metal-containing nodes and organic linkers through coordination bonds.1 Due to their structural and functional tunability, MOFs have found application in a variety of areas including gas storage, separation, chemical sensing, catalysis, energy harvesting, and biomedicine.2 Many early MOFs are composed of single metals and organic linkers. However, as the application scope of MOFs continues to expand, simple MOF structures based on single metals with organic linkers are far from enough to satisfy the greater requirements. Quests for advanced functionalities in MOFs inevitably require more complex structures and pore environments. In a review paper, Yaghi and coworkers proposed that future MOF materials will have multiple building units arranged in specific sequences within a MOF crystal.3 Kitagawa also predicted that the next generation of porous materials would ideally possess features including hierarchy and hybridity, anisotropy and asymmetry, and disorder and defects.4 Constructing MOFs from multiple components is one way to achieve complex structures with sophisticated applications.5 The ability to arrange multiple metals and organic functional groups in desired proximity with atomic precision in a periodic lattice is expected to promote fascinating developments in basic sciences and applications. For example, the combination of diverse metals and functional groups in a multi-component

MOF can lead to emergent synergistic effects in catalysis and gas adsorption.6 A simple approach towards multi-component MOFs is to adopt a series of organic linkers that have the same length, geometry, and connectivity but different functional groups. These linkers uniformly distribute within the same framework forming multivariate MOFs (MTV-MOFs) with emergent properties.7 However, randomly distributed linkers and functional groups have posed a challenge in structural characterization. X-ray diffraction, a powerful technique to determine MOF structure, does not show the sequence of functional groups because of the substitutional disorder of linkers. To map the multiple functional groups within an MTV-MOF, solid state NMR in combination with molecular modelling techniques need to be adopted.8 To combat disorder, one possible strategy is to use a lowsymmetry MOF as a matrix. A set of linkers with different symmetry and/or connectivity can be placed at predetermined positions within the symmetry-reduced lattice. These linkers can be easily differentiated from each other by single-crystal X-ray crystallography so that the position of the functional group on each linker can be precisely located. This strategy has been well demonstrated by Telfer and coworkers who reported the one-pot synthesis of a family of isoreticular MOFs with three crystallographically distinct linkers.9 Considering that multiple phases can be formed in a multi-component system, it is exceedingly difficult to control the structure and phase purity of the product in a one-pot reaction. To take control over the formation of mixed-linker MOFs, we recently developed a stepwise synthetic method named sequential linker installation.10 This strategy utilizes a stable MOF with inherent coordinatively unsaturated sites as a matrix11 and postsynthetically installs linkers into the defects to form mixed-linker MOFs. The open MOF matrix allows the sequential installation of two linkers with different lengths.12 The exploration of the linker installation method has led to the discovery of various tertiary and quaternary MOFs with controllable pore environments and emerging properties in gas storage and catalysis.13 Very recently, Zhang and coworkers have reported the insertion of three linkers in a ZrMOF, resulting in a quinary MOF with ordered arrangement of framework fragments.14 Still, it is challenging to rationally design a MOF matrix that can accommodate three or more secondary linkers. To further enhance the complexity of MOFs, asymmetric linkers may be employed, which tend to form symmetry-reduced MOFs to accommodate multiple linkers arranged in crystallographically determined sequences. Bearing this in mind, we designed a carbazole-based linker to form a matrix with three

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different coordination vacancies. Sequential linker installation was subsequently carried out to insert three linear linkers with different lengths and functional groups into each coordination vacancy. As a result, a series of quinary MOFs with five crystallographically ordered components (i.e. four different linkers and a Zr6 cluster) were obtained, representing a highest degree of complexity at a predetermined array within the crystal lattice. These quinary MOFs provide a nearly ideal platform to incorporate multivariate functionalities within a complex pore environment.

unsaturated Zr sites on the equatorial plane. These unsaturated Zr sites were capped by four pairs of terminal H2O/-OH- groups to balance the charge.16 The terminal H2O/-OH- groups may be replaced through an acid-base reaction with linear carboxylate linkers.11 Theoretically, each pair of adjacent Zr-clusters can be further connected by linear linkers of proper length along the aaxis and c-axis (Figure 1e and g, colored blue and green respectively). Therefore, two linear linkers with different lengths can be incorporated in the pocket along the a- and c-axes. PCN-606 provides a blueprint for the design of more complex MOF matrices that can accommodate three linear linkers. We propose that the trapezoidal linkers will form MOFs with lower symmetries so that three linear linkers can be arranged at different positions in the symmetry-reduced crystal lattice. To this end, a carbazole-based linker (L2) was designed as the trapezoidal analogue of L1. By replacing the rectangular biphenyl groups with a trapezoidal carbazole moiety, the symmetry of linker was reduced from C2h to Cs (Figure 1b). As expected, the reaction of Zr4+ and L2 gives rise to a MOF isostructural to PCN-606 but with reduced symmetry (Figure 1d). The MOF of lower symmetry was named PCN-609. Although the single-crystal structure of PCN-609 still crystallizes in a highly symmetric space group, the unit cell of PCN-609 doubled compared to that of PCN-606 because of the reduced symmetry. The trapezoidal L2 eliminates the 2-fold axis passing through the linker along the c-direction. As a result, two pockets with different sizes were created along the cdirection (Figure 1f). Meanwhile, the pocket along the a-direction was maintained (Figure 1h). Theoretically, three linkers with different lengths can be incorporated into PCN-609.

Figure 1. (a) The biphenyl-based rectangular linker (L1) and (b) carbazole-based trapezoidal linker (L2). Schematic representation of MOFs formed by L1(c) and L2 (d). Single crystal structure of MOFs formed by L1 and L2 viewed along a-direction (e,g) and cdirection (f,h). Pocket I, II, and III are colored blue, yellow, and green, respectively. To carry out linker installation, a Zr-based MOF with inherent coordinatively unsaturated metal sites is used as a matrix. In our previous research, a series of MOFs with 8-connected Zr6 clusters and tetratopic linkers (Figure 1a) were synthesized, which represent suitable platforms to accommodate secondary linkers.15 By combining tetratopic linkers and 8-connected Zr6 clusters, a {4,8}-connected scu network is expected, namely PCN-606 (Figure 1c). Single-crystal X-ray diffraction experiments have revealed that the PCN-606 series crystallizes in the orthorhombic space group Cmmm. Each Zr6 cluster in PCN-606 is coordinated to eight carboxylate ligands, leaving eight coordinatively

Figure 2. Single-crystal to single-crystal transformation of (a) PCN-606 by installation of (b) BDC, (c) TPDC and a combination thereof (d).


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Journal of the American Chemical Society

Figure 3. Single crystal structures of PCN-609 (a) and its derivatives PCN-609-BDC (b), PCN-609-BPDC (c), PCN-609-TPDC (d), PCN609-BDC-BPDC (e), PCN-609-BDC-TPDC (f), PCN-609-BPDC-TPDC (g), and PCN-609-BDC-BPDC-TPDC (h). To prove our hypothesis, linkers with different lengths were sequentially installed in PCN-606 and PCN-609. By incubating PCN-606 crystals in DMF solutions of the linear linkers, the coordinatively unsaturated Zr cluster further binds to carboxylate linkers, leading to the insertion of linkers to the empty pocket. Single-crystal to single-crystal transformation was realized so that the positions of subsequently installed linkers were unambiguously observed in the crystallographically resolved structures. For example, incorporation of BDC into PCN-606 (Figure 2a) leads to the formation of PCN-606-BDC (Figure 2b) which can be further transformed into PCN-606-BDC-TPDC (Figure 2d) when treated with TPDC solution (BDC = 1,4benzenedicarboxylate, TPDC = 2',5'-dimethylterphenyl-4,4''dicarboxylate). The sequence of linker installation does not affect the structure of the final product. PCN-606-TPDC (Figure 2c) can be initially formed and subsequently transformed into PCN-606BDC-TPDC. In fact, the installation process of two linkers are orthogonal so that two linkers can be incorporated simultaneously by reacting with a solution of BDC and TPDC. In total, two linkers can be postsynthetically installed into PCN-606. PCN-609 contains three pockets with different sizes, which potentially allows the installation of three linkers with different

lengths. The sequence of linker installation is critical for the successful incorporation of all three linear linkers. The rigid pockets I and II are suitable for BDC and BPDC respectively. However, the framework structures are flexible along the c-axis, so that pocket III can adapt to tolerate the installation of linkers with lengths ranging from 11.2 Å (BPDC) to 15.2 Å (TPDC). To restrain pocket III from being occupied by the shorter linker BPDC, TPDC should be installed prior to BPDC. The TPDC will occupy pocket III, leaving pocket I and II poised for BDC and BPDC, respectively (Figure 3d,e). However, if BPDC is initially installed, it will occupy both pocket II and pocket III (Figure 3c,f). As a result, TPDC would not be successively incorporated. In total, seven different MOFs can be derived by the installation of three linear linkers or a combination thereof. These includes PCN-609-BDC, PCN-609-BPDC, PCN-609-TPDC, PCN-609BDC-BPDC, PCN-609-BDC-TPDC, PCN-609-BPDC-TPDC, and PCN-609-BDC-BPDC-TPDC (BPDC = biphenyl-4,4'dicarboxylate). Single crystals of these MOFs were successfully isolated. The structures and compositions of the MOFs were determined by single crystal X-ray diffraction and confirmed by 1 H-NMR of digested samples (Figure S5-S12). The bulk samples were characterized by powder X-ray diffraction, indicating the



phase purity and the maintained crystallinity after treatments. The N2 adsorption measurements further show that the porosity and BET surface area of PCN-609 was well-maintained and controlled after the installation of different linkers (Figure S34, Table S3). It should be noted that the stepwise linker installation process is necessary for the formation of these multi-component MOFs. We attempted to synthesize mixed-linker Zr-MOFs starting from a combination of L2 and other linear linkers through a one-pot synthetic approach; however, UiO structure impurities were formed by the linear linkers. In the one-pot synthesis, the competitive formation of different products makes it exceedingly challenging to obtain the desired mixed-linker MOFs.

generate complex pore environments for a wide range of applications. In conclusion, a multivariate quinary MOF system was constructed from a low-symmetry MOF matrix. A judiciously designed trapezoidal linker reduced the overall symmetry of the frameworks so that three pockets with different lengths were created. By postsynthetic installation of three linkers with proper lengths and in proper order into the open matrix, quinary MOFs with multivariate pore environments were obtained. Single crystal structures clearly show the structural transformation during the stepwise insertion of linkers. Besides providing a complicated yet high controllable multivariate MOF system, this work also highlights the importance of symmetry-reduced linkers on the formation of sophisticated pore environments. A greater exploration of ligands with lower symmetry, either in respect to their geometry, functional group position, or type of coordinating groups, will lead to the discovery of more multi-component framework architectures.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Text, tables, and figures giving experimental procedures for the syntheses of the ligands and MOFs, PXRD, N2 adsorption isotherms, 1H NMR spectra, and other additional information (PDF) X-ray crystallographic details of PCN-606, PCN-606-BDC, PCN606-TPDC, and PCN-606-BDC-TPDC (CIF) X-ray crystallographic details of PCN-609, PCN-609-BDC, PCN609-BPDC, PCN-609-TPDC, PCN-609-BDC-BPDC, PCN-609BDC-TPDC, PCN-609-BPDC-TPDC, PCN-609-BDC-BPDCTPDC, PCN-609-BDC-BPDC-EDDB, and PCN-609-BDCBPDC-AZDC (CIF)

AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected] Figure 4. Schematic representation of PCN-609 (a) with pockets I (b), II (c), and III (d) able to accommodate a variety of functionalized linkers. Among these multi-component MOFs, PCN-609-BDC-BPDCTPDC shows the highest degree of complexity with four different linkers arranged at crystallographically distinct positions in the periodic lattice. It provides a nearly ideal platform to precisely control the pore environment by placing different linkers with specific functionalities. We show that a series of functional groups can be integrated through each of the three linkers forming multivariate MOFs (Figure 4a). Pocket I can accommodate BDC and its derivatives (Figure 4b), while pocket II can fit BPDC with different functional groups (Figure 4c). Furthermore, the flexible pocket III allows for a wider range of linkers with different lengths to be installed (Figure 4d and S33). As shown in Figure 4, linear linkers with different lengths and functionalities were successfully installed in PCN-609 as confirmed by powder X-ray diffraction and 1H-NMR digestion experiments (Figure S13-S29 and S37, Table S1). Furthermore, single crystal structures of PCN-609-BDC-BPDC-EDDB and PCN-609-BDC-BPDC-AZDC were successfully obtained. Theoretically, 447 MOFs are expected from the combinations of linkers in the list. The almost unlimited tunability of the PCN-609 system is expected to

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT The gas sorption studies were supported by the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DESC0001015). Structural analyses were supported by the Robert A. Welch Foundation through a Welch Endowed Chair to HJZ (A0030). The National Science Foundation Graduate Research Fellowship (DGE: 1252521) is gratefully acknowledged. The authors also acknowledge the financial support of the U.S. Department of Energy Office of Fossil Energy National Energy Technology Laboratory (DEFE0026472) and National Science Foundation Small Business Innovation Research (NSF-SBIR) program under Grant No. (1632486). S. Yuan also acknowledges the Dow Chemical Graduate Fellowship.

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