by Markus J. Kalmutzki, Nikita Hanikel, and Omar M. Yaghi

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Presentation transcript:

by Markus J. Kalmutzki, Nikita Hanikel, and Omar M. Yaghi Secondary building units as the turning point in the development of the reticular chemistry of MOFs by Markus J. Kalmutzki, Nikita Hanikel, and Omar M. Yaghi Science Volume 4(10):eaat9180 October 5, 2018 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 1 Impact of the SBU on the structure, chemistry, and applications of MOFs. Impact of the SBU on the structure, chemistry, and applications of MOFs. The rich structural chemistry of MOFs is founded on the structural diversity of the SBUs. Furthermore, the structural rigidity of the SBUs renders MOFs mechanically and architecturally stable, and thus permanently porous. The chemical nature of SBUs gives rise to “framework chemistry”—the post-synthetic chemical modification of MOFs—and is key to further extending their applications. Chemical modifications include substitution reactions of linkers and terminal ligands, metallation reactions, and metal ion exchange reactions. Prominent applications of MOFs that profit from the chemical nature of the SBU are gas and vapor adsorption, separations, and catalysis. Markus J. Kalmutzki et al. Sci Adv 2018;4:eaat9180 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 2 The reticular table. The reticular table. A table of possible bipartite nets representing binary frameworks made by reticular chemistry. All topologies are shown as their corresponding augmented net. If more than one net exists, then the identifier of the indicated net is shown in bold. In these cases, either the local symmetry of the building units (for example, torsion angles and dihedral angles) or the comparison of the maximum symmetry embedding and the topological density helps to decide which net is most likely to form from the given set of building units. The edge-transitive nets are the most likely products of reticular synthesis and are shown on a white background. The light gray fields indicate possible non–edge-transitive nets for a given combination of building units. All identifiers are given in alphabetical order. All data shown are taken from the Reticular Chemistry Structure Resource (23 March 2018) (110) and were collected using the search routines for the respective combination of vertices. Markus J. Kalmutzki et al. Sci Adv 2018;4:eaat9180 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 3 Complexity in MOFs through the multi-SBU approach. Complexity in MOFs through the multi-SBU approach. (A) Crystal structure of [M3OL3]2(TCPP-M)3 with an underlying stp topology. The well-mixed scenario (mixed-metal SBUs; left) is observed for metals with similar radii and electronegativity (for example, Fe2+ and Ni2+). In contrast, for metals with significantly different radii and electronegativity (for example, Mn2+ and Fe2+), the domain scenario (right) is observed. (B) Crystal structure of FDM-3. The two different binding groups of the PyC linker lead to the formation of octahedral Zn4O(-COO)6 and Zn4O(-COO)5(NN) SBUs and trigonal Cu3(μ3-OH)(OH)3(PyC)3 SBUs, which show interesting redox chemistry. (C) The TBU approach allows the targeted synthesis of highly complex structures. Here, metal-organic polyhedron-1 (MOP-1; rco) TBUs are linked by trigonal Cu3OL3(tetrazolate)3 SBUs to give a MOF of rht topology. The formation of the TBU (left) and further linking into an extended structure (right) are shown. Markus J. Kalmutzki et al. Sci Adv 2018;4:eaat9180 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 4 Ligand and linker exchange reactions in MOFs. Ligand and linker exchange reactions in MOFs. (A) The capping formate ligands on the octanuclear Al8(OH)8(HCOO)4(-COO)12 SBUs can be exchanged with molecules bearing appropriate binding groups. Here, the alignment of (+)-jasmonic acid is shown. The chiral framework serves as a reference for the determination of the absolute configuration of the aligned molecule by x-ray crystallography. (B) In a similar manner, the capping formate ligands can be replaced by linear ditopic BPDC linkers to afford a transformation of the fon topology (MOF-520) into the skl topology (MOF-520-BPDC). MOF-520-BPDC exhibits enhanced mechanical stability compared to pristine MOF-520. (C) The architectural stability provided by the SBUs allows the formation ordered vacancies, as exemplified by the topological transformation of the pcu topology framework Zn4O(PyC)3 into the srs framework [Zn3□(OH)(Pyc)1.5□1.5(OH)(H2O)3.5](PyC)0.5. Addition of metal ions and linkers regenerates the pcu framework, and by using functionalized linkers, an ordered arrangement of functionalities can be realized. Markus J. Kalmutzki et al. Sci Adv 2018;4:eaat9180 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 5 Adsorption on SBUs. Adsorption on SBUs. (A) Selection of SBUs with potential open metal sites. (i) M2L2(-COO)4, (ii) M3OL3(-COO)6, (iii) M4L4Cl(tetrazolate)8, (iv) Cu3OL3(PyC)3, and (v) {M3[O3(-COO)3]}∞. These sites feature large unoccupied orbitals that can interact strongly with adsorbent molecules and are commonly generated by heating the MOF in dynamic vacuum. (B) Crystal structure of HKUST-1. The tbo framework features one of the highest densities of open metal sites in MOFs; consequently, HKUST-1 has one of the highest methane storage capacities among all MOFs. (C) CO2 adsorption on the open metal sites in MOF-74. The polarizing nature of the open metal sites leads to a high selectivity for CO2 over N2. Strong interactions are evidenced by the nonlinear geometry of CO2 in the chemisorbed state. (D) Adsorption of CO2 in mmen-Mg2(DOBPDC) following a cooperative insertion mechanism that allows adsorption-desorption cycles to be realized under mild TSA conditions. (E) Covalent capture of CO2 on the -OH functionalized SBUs of MAF-X25-ox as bicarbonate. This adsorption mechanism facilitates both a high capacity and a high selectivity for CO2. (F) Adsorption of water in the tetrahedral pore of MOF-801. The bridging μ3-OH groups of the Zr6O4(OH)4(-COO)12 SBUs act as primary adsorption sites by hydrogen bonding. Markus J. Kalmutzki et al. Sci Adv 2018;4:eaat9180 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 6 SBUs as catalytic centers. SBUs as catalytic centers. (A) Cation exchange in MFU-4l generates Ni-MFU-4l, a catalyst for selective conversion of ethylene to 1-butene. (B) Metallation of NU-1000 with copper using the AIM method results in Cu-NU-1000. A Cu-oxo cluster is proposed to form between two Zr-SBUs, which shows high activity for methane oxidation. (C) Immersing MOF-808 in sulfuric acid yields the super acidic MOF-808-2.5SO4, which was demonstrated to be active in the Brønsted acid–catalyzed isomerization of α-pinene to camphene. (D) Pre-synthesized mixed-metal SBUs provide access to photocatalytically active MOFs such as PCN-415-NH2. In the presence of TEOA as a sacrificial donor (S), the nanocomposite Pt@PCN-415-NH2 shows high activity for photocatalytic hydrogen evolution reactions. Markus J. Kalmutzki et al. Sci Adv 2018;4:eaat9180 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).