Communication pubs.acs.org/crystal
4,6-Connected fsb Topology Networks Obtained through Two-Step Crystal Engineering of Decorated Trigonal Prismatic Nodes Alexander Schoedel,† Michael Jaquier,† Wesley Boyette,† Lukasz Wojtas,† Mohamed Eddaoudi,†,‡ and Michael J. Zaworotko*,†,⊥ †
Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE205, Tampa, Florida 33620, United States Chemical Science, King Abdullah University of Science and Technology, Thuwal 23955-6900, Kingdom of Saudi Arabia ⊥ Department of Chemical and Environmental Science, University of Limerick, Limerick, Ireland ‡
S Supporting Information *
ABSTRACT: A two-step crystal engineering strategy has been utilized to synthesize a new and versatile class of metal−organic materials, the first to exhibit 4,6-connected fsb topology. The new fsb networks are constructed from simple and inexpensive nodes (4-connected Zn(CO2)(py)2 tetrahedra; 6-connected Cr(μ3-O)(RCO2)6 trigonal prisms) and linker ligands (isonicotinate and various dicarboxylates). Further, since interpenetration is precluded, they can exhibit extra-large void volumes. These fsb nets are prototypal for what should ultimately become a large family of related structures given the ready availability of functionalized and/or expanded variants of both linker ligands. The fsb nets described herein therefore represent platforms or blueprints for a new family of ultrahigh surface area porous materials. has resulted in isolation of three fine-tunable platforms exhibiting stp,15 asc,16 and lon-e17 topology, respectively. We herein expand the scope of this two-step crystal engineering strategy by introducing a new platform, the first examples of MOMs with 4,6-c fsb topology. Specifically, a decorated variant of the long known18 Cr(μ3-O)(RCO2)6 cluster was exploited as a trigonal prismatic primary molecular building block (tpPMBB-1) thanks to its decoration by six pyridyl moieties.19 tpPMBB-1 was prepared in step 1, and in step 2 it was solvothermally reacted with Zn(NO3)2 and dicarboxylate linkers, thereby affording two frameworks sustained by tpPMBB-1 and tetrahedral Zn(CO2)2(py)2 nodes linked by 2,5thiophenedicarboxylate (tdc) or 1,4-benzenedicarboxylate (bdc) (Figure 1). The resulting nets are named after their MBBs and the underlying topology as evaluated using TOPOS20 and retrieved from the RCSR database:21 tpPMBB-1-fsb-1 and -fsb-2 for tdc and bdc, respectively. [Zn3(tdc)3[Cr3O(isonic)6(H2O)2(OH)]]·x solv, tp-PMBB1-fsb-1 and [Zn3(bdc)3[Cr3O(isonic)6(H2O)2(OH)]]·x solv (solv = DMF, MeOH) tp-PMBB-1-fsb-2 both crystallize in the hexagonal space group P6/mmm with two formula units per unit cell. Their cell parameters vary slightly, and both networks possess large hexagonal channels along [001] with diameters of 1.4−1.5 nm. The experimental powder X-ray diffraction patterns of both fsb variants match closely with those calculated from the respective single crystal structures (Figure 2). The free volume in these structures was calculated to be 77.2% (fsb-1) and 74.1% (fsb-2) using PLATON.
C
rystal engineering, the rational design and synthesis of functional materials with desired properties, has been a subject of growing interest for over 20 years.1 Whereas crystal engineering initially focused upon the understanding and synthesis of molecular materials, it has also provided important concepts in the development of metal−organic materials (MOMs).2 MOMs are periodic networks assembled from metal ions or clusters and organic multifunctional ligands. In this context, high symmetry networks are of special interest since they are robust from a design perspective, and they can serve as platforms for the systematic study of structure and function. Further, their bottom-up synthesis is facilitated by high symmetry molecular building blocks (MBBs) and follows rational design principles. An initial focus upon single metalnodes and pyridyl linkers was soon followed by study of MOMs based upon polynuclear high-symmetry metal-carboxylate clusters which offered robustness and afforded a new generation of permanently porous materials.3 Shortly after these breakthroughs, MOMs gained additional momentum since, in contrast to other classes of porous materials, they are inherently modular in nature. This makes MOMs amenable to fine-tuning.4 Subsequently, MOMs were developed to address gas purification and storage,5 catalysis,6 small-molecule separations,7 and chemical sensing.8 Carboxylate-based MOMs sustained by polyhedral or polygonal MBBs have already afforded several important families of nets: 4-c dia2a,d and nbo,9 6-c pcu5a,10 and acs,11 3,4-c tbo,12 and 3,24-c rht.13 These nets might be described as platforms since their underlying network topology serves as a blueprint for the generation of families of frameworks by judicious selection of different MBBs. We have recently demonstrated a two-step crystal engineering strategy14 for the generation of novel MOM platforms. This © 2014 American Chemical Society
Received: February 10, 2014 Revised: April 8, 2014 Published: April 9, 2014 2115
dx.doi.org/10.1021/cg500205f | Cryst. Growth Des. 2014, 14, 2115−2117
Crystal Growth & Design
Communication
Figure 1. Self-assembly of tp-PMBB-1-fsb-1 from tp-PMBB-1, a tetrahedral Zn(CO2)(py)2 node and a linear dicarboxylate ligand in a 1:3:3 ratio. The different edges (ligands) are shown in red and green. Hydrogen atoms are omitted for clarity.
Figure 3. Self-assembly of tp-PMBB-1-fsb-1 from tp-PMBB-1 and the [Zn6(dicarboxylate)6] SBB. The closely related topologies alb and fsb (shown as augmented versions) are highlighted. Hydrogen atoms are omitted for clarity.
in MOMs based on 6- and 12-connected cluster MBBs.22 However, we note here that our 12-c [Zn6(dicarboxylate)6] SBB is modular and can be sustained by 2,5-furandicarboxylate or 1,4-benzenedicarboxylate moieties, respectively. The angles subtended by the carboxylate moieties in the organic linkers are almost linear or liners (175° and 180°, respectively). We therefore believe that a description based on the binodal, edgetwo transitive fsb topology is appropriate since both nodes and both edges are taken into account. This is supported by recent findings of O’Keeffe and Yaghi, suggesting that deconstructing the overall topology can afford valuable information for crystal engineering of new porous materials.23 The fsb topology of the underlying net can therefore be described as binodal, because of the presence of trigonal prismatic and tetrahedral vertices, and edge-two transitive, because of the presence of isonicotinate and dicarboxylate linkers. These networks represent the first examples of fsb
Figure 2. Experimental and calculated powder X-ray diffraction patterns (background corrected) of tp-PMBB-1-fsb-1 and fsb-2.
The frameworks reported herein can also be regarded as having been built by direct linking of [Zn(CO2R)2(py)2] tetrahedral MBBs through linear (or slightly angular) dicarboxylate linkers to form [Zn6(dicarboxylate)6] supermolecular building blocks (SBBs)13a (Figure 3). These SBBs can then be simplified to a 12-c node that are in turn connected to the pyridyl moiety of the [Cr3(μ3-O)(RCO2)]6 MBBs. The resulting 6,12-c net exhibits binodal, edge-transitive alb topology (Figure 3, middle) that has been previously reported 2116
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Communication
topology MOMs; however, the topology had been predicted.21 It is noteworthy that networks with fsb topology are not selfdual; i.e., interpenetration is inherently precluded. We note here that the 120° angle subtended at the SBB appears to be critical to afford fsb networks since we have observed that slight changes from this angle can result in different topological outcomes that will not be further discussed herein. The networks reported herein are stable in common organic solvents including DMF, methanol, and acetonitrile. However, they are unstable with respect to removal of guests under a vacuum, which we attribute to the flexible nature of the trigonal prismatic MBB as first seen in acs topology nets.11,14b In contrast to our previously reported platforms based upon tpPMBB-1 (asc16 and lon-e17), breathing in fsb-nets is not restricted by other components of the structure, and this might be what facilitates framework collapse. In summary, we have further demonstrated that a two-step crystal engineering approach which is based upon decorated trigonal prismatic MBBs can be used to generate novel families of frameworks or platforms. The networks reported herein are the first examples of MOMs with fsb topology, and we have demonstrated that isoreticular principles can be applied to such nets. We anticipate that the modularity of fsb nets will be high and that it will lead to a plethora of derivatives. Further, given that interpenetration is precluded and that there is ready availability of linear dicarboxylate variants, fsb nets could be ideally suited for study in the context of ultrahigh surface area materials that exhibit mesopores. This will be the subject of future studies.
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ASSOCIATED CONTENT
S Supporting Information *
Complete single-crystal data (CIF), X-ray powder diffraction, infrared spectroscopy, and thermogravimetric analysis data. This material is available free of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Notes
The authors declare no competing financial interests.
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ACKNOWLEDGMENTS This work was partially supported by Award No. FIC/2010/06, made by the King Abdullah University of Science and Technology (KAUST).
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REFERENCES
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