Programmable Topology in New Families of Heterobimetallic Metal

metals, we control the assembly and topology of up to three different inorganic SBUs in ... supramolecular building blocks (SBBs), limiting the basis ...
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Programmable Topology in New Families of Heterobimetallic Metal-Organic Frameworks Patrick F. Muldoon, Chong Liu, Carson C. Miller, Samuel Benjamin Koby, Michael O'Keeffe, Tian-Yi Luo, Nathaniel L Rosi, Sunil Saxena, and Austin Gamble Jarvi J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b02192 • Publication Date (Web): 03 May 2018 Downloaded from http://pubs.acs.org on May 3, 2018

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Journal of the American Chemical Society

Programmable Topology in New Families of Heterobimetallic Metal-Organic Frameworks Patrick F. Muldoon,† Chong Liu,† Carson C. Miller,† S. Benjamin Koby,† Austin Gamble Jarvi,† Tian-Yi Luo,† Sunil Saxena,† Michael O’Keeffe,‡ and Nathaniel L. Rosi*†§ †

Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260

‡

School of Molecular Sciences, Arizona State University, Tempe, AZ 85287

§

National Energy Technology Laboratory, U.S. Department of Energy, Pittsburgh, PA 15236

Supporting Information Placeholder ABSTRACT: Using diverse building blocks, such as different heterometallic clusters, in metal-organic framework (MOF) syntheses greatly increases MOF complexity and leads to emergent synergistic properties. However, applying reticular chemistry to syntheses involving more than two molecular building blocks is challenging and there is limited progress in this area. We are therefore motivated to develop a strategy for achieving systematic and differential control over the coordination of multiple metals in MOFs. Herein, we report the design and synthesis of a diverse series of heterobimetallic MOFs with different metal ions and clusters severally distributed throughout two or three inorganic secondary building units (SBUs). By taking advantage of the bifunctional isonicotinate linker and its derivatives, which can coordinatively distinguish between early and late transition metals, we control the assembly and topology of up to three different inorganic SBUs in one-pot solvothermal reactions. Specifically, M6(μ3O)n(μ3-OH)8-n(CO2)12 (M=Zr4+,Hf4+,Dy3+) SBUs are formed along with metal-pyridyl complexes. By controlling the geometry of the metal-pyridyl complexes, we direct the overall topology to produce eight new MOFs with fcu, ftw, and previously unreported trinodal pfm crystallographic nets.

The myriad properties and applications of metal-organic frameworks (MOFs) largely result from the structural and functional diversity that can be deliberately incorporated by applying the principles of reticular chemistry.1-2 Heterometallic cluster-based MOFs represent a step-change in the structural and compositional diversity and functional complexity of MOF materials which cannot be fully realized until a set of reliable design principles has been established. Heterometallic MOFs, in which two or more different metal ions are periodically segregated throughout a lattice, can lead to emergent synergistic properties and functionalities such as sequential reaction catalysis and ratiometric sensing.3-7 Heterometallic MOFs have been

prepared through postsynthetic metalation,8 postsynthetic metal metathesis,9 and core-shell growth10. In these cases, a preexisting monometallic MOF is augmented by a second metal. In contrast, in heterometallic cluster-based MOFs different metals are severally incorporated into the inorganic secondary building units (SBUs) that constitute the nodes of the MOF’s crystallographic net.11-17 Heterometallic cluster-based MOFs remain relatively unexplored due to complications that arise when applying reticular chemistry to more than two building blocks (e.g. two metals plus linker), and reported work has been more empirical than systematic, with one or two structures in a given publication. A notable exception is the work of Zaworotko et al. in which Cr3-oxo carboxylate clusters terminating in pyridyl groups are synthesized and subsequently combined with various different metals and organic linkers to form a series of heterometallic MOFs.18-22 This two-step method allows independent control over the coordination of different metals without complications arising from three or more molecular building blocks in one-pot reactions. However, this approach requires stable, soluble supramolecular building blocks (SBBs), limiting the basis set of potential SBUs and metals. Ultimately, the range and rate of discovery of heterometallic cluster-based MOFs will greatly improve if rational design can be applied to conventional one-pot solvothermal reactions involving commercially available metal salts and organic linkers. To this end, we believe one-pot approaches relying on bifunctional linkers will be instrumental. It has been established that in reactions involving just one type of metal, bifunctional linkers can facilitate the formation of different inorganic SBUs in situ.23 In more recent examples, the different functional groups of bifunctional linkers discriminate between two metal ions through differential binding affinities.12-14, 24-26 This potentially powerful strategy has yielded a handful of structures but has not been generalized and used to prepare a series of new MOFs comprising diverse collections of heterometallic SBUs. We aimed to expand this linker mediated strategy and establish a modular synthetic platform for the formation of a variety of topologies

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and metal combinations through directed synthesis. Here, we combine a bifunctional linker, isonicotinic acid (INA), and its derivatives with one oxophilic, hard-acid metal ion (Zr4+,Hf4+,Dy3+) and a second softer metal ion (Co2+,Cun+,Ni2+,Fe3+,Cd2+) to form structures where the isonicotinate carboxylate group exclusively coordinates to the former and the nitrogen to the latter. This predictable metal-ligand pairing combined with well-established coordination complexes formed between the various metal-ligand pairs allowed us to prepare a new MOF with three different inorganic SBUs and unprecedented trinodal pfm27 topology as well as to target specific topologies through rational design. In total we report eight new multicomponent MOFs with three different topologies, each containing two or three inorganic SBUs. We believe that these results can inform a general synthetic strategy toward achieving diverse classes of heterometallic cluster-based MOFs. We began by using copper due to its well-known proclivity for forming complexes with nitrogen donor ligands and zirconium as an ideal oxophilic hard acid. Copper can form either square planar or tetrahedral complexes with pyridyl ligands depending on its oxidation state. In addition, dimethylformamide (DMF) is known to reduce metal ions in the presence of water and heat.28 Considering these various copper-pyridyl binding possibilities together with the ubiquitous Zr6(μ3-O)4(μ3-OH)4(CO2)12 SBU of the UiO MOF series,29 we combined Cu(NO3)2 and ZrCl4 with INA in DMF at 120℃ to yield green square prismatic single crystals (Figure S2.1) of MOF1210(Zr/Cu)30-31 with an unprecedented trinodal (12,4,4)-connected net, pfm (Figure 1). MOF-1210(Zr/Cu) contains all three of the coordination modes described above; Zr6-oxo clusters (Figure 1A), tetrahedral Cu1+(NC5H4CO2-)4 (Figure 1B), and square planar Cu2+(NC5H4CO2-)4 (Figure 1C). The coordination environment of the Cu2+ SBU was confirmed by electron paramagnetic resonance (Figure S2.6). The Cu1+ tetrahedral and Zr6-oxo clusters are integrated in an (8,4)-connected augmented flu32 net (flu-a, Figure 1D). If we bisect a typical flu-type structure along the tetrahedral nodes, the intermittent layers of Zr6-oxo clusters are arranged in 2-D square lattices (sql33). Interconnecting Zr6-oxo clusters within each of these 2D layers are the square planar Cu2+ nodes, thus completing the augmented pfm net (pfm-a, Figure 1E). Surprisingly the carboxylate groups stemming from the square planar Cu2+ nodes do not exhibit the bridging motif of most Zr6-oxo based MOFs but instead form a single Zr-O bond; this may be explained by steric crowding around the Cu2+ sites, which forces the pyridyl rings and by extension the carboxylate groups to be nearly perpendicular to the CuN4 square. MOF-1210(Zr/Cu) exhibits permanent porosity, with BrunauerEmmett-Teller (BET) surface area of 630 m2 g-1 (Figure S2.4). To our knowledge, this is a rare example of a MOF containing discrete Cun+(pyridyl)4 nodes which retains crystallinity (Figure S2.5) and porosity after activation. We note that overall stability may stem from incorporation of robust Zr6-oxo carboxylate clusters throughout the framework and this phenomenon of leveraged stability may provide a means for incorporating less stable yet functional metal nodes into MOFs for specific applications. Another notable feature of this synthesis is that while crystalline MOFs composed of the Zrcarboxylate motif typically require a large excess of acid to compensate for rapid and irreversible binding between Zr4+ and O-donor ligands, this synthesis produces large single crystals without additional reagents, suggesting that the high reversibility of the Cu-pyridyl binding enables the overall system to access a highly ordered thermodynamically favorable product.

Figure 1. MOF-1210 structure. (A) Zr SBU (Zr4+, dark green; C, dark grey; bridging O, red; monodentate O, orange; H not shown). Left: Zr6(μ3-O)4(μ3-OH)4 core. Center: Zr6(μ3-O)4(μ3-OH)4(CO2)12 cluster in which green octahedron defines Zr6 core. Right: polyhedral representation of SBU. (B) Tetrahedral Cu1+(NC5H4CO2-)4 SBB (Cu1+; dark blue; N, light blue; CuN4, blue tetrahedron). (C) Square planar Cu2+(NC5H4CO2-)4 SBB (CuN4, red square, NC5H4CO2ligands are twofold disordered and only one position is shown). (D) flu-a net, elongated along z axis. (E) pfm-a net. (F) MOF1210(Zr/Cu) crystal structure. MOF-1210 is also of note from a topological perspective. In the designed synthesis of MOFs, the principal targets are structures with simple underlying nets. Nets are characterized by a transitivity p q : p kinds (i.e. symmetry-related) of vertex (node) and q kinds of edge (link). The principle of minimal transitivity states that for a given number of kinds of vertex, the number of kinds of edge is usually the minimum possible.34 Representative examples of MOFs adopting minimal transitivity with one kind of link (transitivity 1 1 and 2 1) are enumerated in the Supporting Information (Figure S2.7a-c). For structures based on nets with transitivity 3 2, there can be a polytopic linker with multiple branch points linked to one kind of inorganic SBU, or there can be a polytopic linker joining two different inorganic SBUs (Figure S2.7d,e).34 The final possibility (Figure S2.7f) is three different inorganic SBUs joined by ditopic linkers and we believe MOF-1210 to be the first such example. Indeed, we know of only one other MOF with three different inorganic SBUs, but this has a structure based on the ott net with transitivity 3 4: four distinct kinds of link rather than the minimum of two.11

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Journal of the American Chemical Society To further establish the rational design of multicomponent heterometallic cluster-based MOFs via this linker-directed approach, we next chose to combine Zr4+, INA, and a different soft metal ion that we expected to exclusively form square nodes with the pyridyl groups. Specifically, Co2+ is known to form a trans-octahedral complex with pyridine (py) of the formula CoCl2(py)4.35 An analogous complex based on INA linkers rather than py would be comparable to the planar tetracarboxylate linkers that have been connected with Zr6-oxo clusters to form MOFs with augmented ftw36 topology (ftw-a, Figure 2D) such as MOF-52537 and NU-1100-1105.38-40 By combining Co(NO3)2 and ZrCl4 with INA in DMF at 100℃, we formed violet cubic crystals (Figure S3.1) with the expected ftw topology, MOF-1211(Zr/Co)30-31 (Figure 2). To our knowledge this is the first example of a Zr-MOF with ftw topology where the square node is formed in situ and does not require pre-synthesized tetratopic organic linkers. The CoCl2(NC5H4CO2-)4 moiety in MOF-1211(Zr/Co) is essentially a supramolecular tetracarboxylate linker (Figure 2A). Unlike the square SBBs in MOF-1210(Zr/Cu), the carboxylate groups in MOF1211(Zr/Co) are coplanar with the square and thus bind to the Zr6oxo clusters in a bridging mode (Figure 2B): this is most likely due to the longer Co2+-N bond length, 2.24 Å, compared with 2.005 Å Cu2+-N bond length in MOF-1210(Zr/Cu). MOF-1211(Zr/Co) also exhibits permanent porosity (BET 925 m2 g-1, Figure S3.4).

observed in MOF-1210 and MOF-1211 and instead promote formation of the unique linear inorganic SBB, trans-square planar CuCl2(NC6H6CO2-)2, which connects Zr6-oxo/Hf6-oxo clusters in the same augmented fcu42 topology as the now ubiquitous UiO series29 (fcu-a, Figure 3D). Unlike MOF-1210 and MOF-1211, we could not establish permanent porosity in MOF-1212 which may be explained by the correlation between overall MOF stability and the degree of connectivity of the inorganic SBUs, ceteris paribus.

Figure 3. MOF-1212 structure. (A) Top: linear CuCl2(NC6H6CO2-)2 SBB (Cu2+, dark blue; N, light blue; Cl, light green; C, dark grey; O, red; H atoms omitted; methyl groups on NC6H6CO2- ligands are twofold disordered and only one position is shown). Bottom: simplified representation of SBB with methyl groups omitted and large blue sphere replacing CuCl2. (B) Hf SBU. Left: Hf6(μ3-O)4(μ3OH)4(CO2)12 cluster (Hf4+, dark green) in which green octahedron defines Hf6 core. Right: polyhedral representation of SBU. (C) MOF1212(Hf/Cu) crystal structure. (D) fcu-a net.

Figure 2. MOF-1211 structure. (A) Square planar CoCl2(NC5H4CO2)4 SBB (Co2+, dark blue; N, light blue; Cl, light green; C, dark grey; O, red; CoCl2N4, blue squares; H atoms omitted; NC5H4CO2- ligands are twofold rotationally disordered and only one position is shown). (B) Zr SBU. Left: Zr6(μ3-O)4(μ3-OH)4(CO2)12 cluster (Zr4+, dark green) in which green octahedron defines Zr6 core. Right: polyhedral representation of SBU. (C) MOF-1211(Zr/Co) crystal structure. (D) ftw-a net.

Given the apparent role of steric hindrance in the geometry of the monometallic nodes in MOF-1210 and MOF-1211, we employed 2methyl-INA expecting the methyl group to inhibit coordination of four pyridyl ligands around a single metal ion. We note that coordination complexes of the structure trans-[CuCl2(3-X-pyridine)2] (X=Cl,Br) have been reported.41 By replacing the halopyridine ligands with 2methyl-INA, the resulting complex constitutes a supramolecular linear dicarboxylate linker (Figure 3A). Cu(NO3)2 and ZrCl4 were combined with 2-methyl-INA in DMF at 85℃ to yield light blue octahedral crystals (Figure S4.1) of MOF-1212(Zr/Cu)30-31. By substituting HfCl4 for ZrCl4 under similar conditions, the isostructural analogue, MOF1212(Hf/Cu), was formed (Figure S4.2) as higher quality crystals suitable for single crystal X-ray diffraction (Figure 3C). We can infer that the methyl groups do prevent the formation of the tetratopic SBBs

After establishing the topological diversity of this approach through the formation of pfm, ftw and fcu nets, we then explored the incorporation of other hard and soft metal ions. Recognizing that oxophilic lanthanide ions have been used to form MOFs with metaloxo clusters analogous to the Zr6-oxo clusters formed in this work,43 we combined DyCl3 and 3-fluoro-INA with various soft metal ions in DMF at 120℃ to form four isoreticular analogues of MOF1211(Zr/Co), MOF-1213(Dy/M) (M=Cd2+,Ni2+,Fe3+,or Co2+)30-31, each having a different metal ion at the 4-connected square node (Figure S5.8). We have designed and synthesized a family of eight new heterometallic cluster-based MOFs in straightforward one-pot solvothermal reactions. Through a bifunctional linker-directed approach we have discovered a new trinodal pfm topology as well as successfully targeted specific binodal topologies, ftw and fcu. In the case of MOF-1211 and MOF-1213, we have demonstrated that the design principles for a given heterobimetallic structure may be transcribed for different metal ion pairs. We expect that these general design and synthesis strategies will lead to the emergence of numerous new multicomponent structures and a concomitant increase in the diversity of functions and applications of MOFs.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website.

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Experimental details and additional data (PDF) Crystallographic data for MOF-1210(Zr/Cu) CCDC 1823098 (CIF) Crystallographic data for MOF-1211(Zr/Co) CCDC 1823101 (CIF) Crystallographic data for MOF-1212(Hf/Cu) CCDC 1823100 (CIF) Crystallographic data for MOF-1213(Dy/Cd) CCDC 1823099 (CIF)

AUTHOR INFORMATION Corresponding Author *[email protected]

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This project received partial support from the Defense Threat Reduction Agency-Joint Science and Technology Office for Chemical and Biological Defense Basic Research (Grant no. HDTRA1-16-10044, NLR). In addition this project was supported in part by an appointment to the Internship/Research Participation Program at the National Energy Technology Laboratory, U.S. Environmental Protection Agency, administered by the Oak Ridge Institute for Science and Education through an interagency agreement between the U.S. Department of Energy and EPA (PFM). The authors also thank the University of Pittsburgh and the Petersen Nano Fabrication and Characterization Facility at the University of Pittsburgh for access to PXRD instrumentation.

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