Enriching the Reticular Chemistry Repertoire with Minimal Edge-Transitive Related Nets: Access to Highly Coordinated Metal–Organic Frameworks Based on Double Six-Membered Rings as Net-Coded Building Units

Chen, Zhijie; Thiam, Zeynabou; Shkurenko, Aleksander; Weseliński, Łukasz J.; Adil, Karim; Jiang, Hao; Alezi, Dalal; Assen, Ayalew H.; O’Keeffe, Michael; Eddaoudi, Mohamed

doi:10.1021/jacs.9b11260

Cited by 52 publications

(48 citation statements)

References 43 publications

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“…Submitted to Chemical Reviews Scheme.1 An illustration of the relationship between parent net and derived/related nets using Al-soc-MOF-1 93 (socderived edq net) and RE-kce-MOF-1 92 (soc-related kce net). Reproduced with permission from reference 92 . Copyright 2019 American Chemical Society.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

“…11,130 The right choice of the polytopic organic linker with the prerequisite building blocks (i.e., hexagon and triangle), in combination with the proper conditions to in-situ generate the RE polynuclear cluster, led to the formation of the targeted MOFs with aforesaid kex net. 92 Interestingly, the introduction of the heterofunctional linkers with both tetrazolate and carboxylate moieties results in the first urx-MOFs based on the RE polynuclear clusters. Aside from the well-studied nonanuclear clusters as the d6R building units, the RE hexanuclear cluster directed by the tetrazolate moieties can be viewed as a trigonal anti-prismatic SBU.…”

Section: Mofs Based On Twf and Twf-derived Netsmentioning

confidence: 99%

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Reticular Chemistry 3.2: Typical Minimal Edge-Transitive Derived and Related Nets for the Design and Synthesis of Metal–Organic Frameworks

et al. 2020

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Reticular chemistry has proven as a notable/distinctive discipline aimed at the deliberate assembly of periodic solids, offering great opportunities to effectively deploy the gained knowledge on net-topologies as a guide and toolbox for designed syntheses, based on the assembly of molecular building blocks into targeted and anticipated structures of crystalline extended solids. The effective practice of reticular chemistry has enriched the repertoire of crystal chemistry and afforded the notable accelerating development of crystalline extended frameworks, especially metal-organic frameworks (MOFs). Here, we review a special class of trinodal MOF structures based on the reticulation of special minimal edgetransitive nets (nets with transitivity [3 2], three distinct nodes and two kind of edges) derived from edge-transitive nets (one kind of edge). The rationale for deriving these special minimal edge-transitive nets is reviewed and their associated net-coded building (net-cBUs) for the design of trinodal MOFs is presented and discussed. The resultant inclusive list of the enumerated minimal edge-transitive nets provides a unique toolbox for the material's designer as it offers ideal blueprints for the deliberate design and rational assembly of building blocks with embedded multiple branch points into intricate trinodal MOFs.

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Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Section: Mofs Based On Twf and Twf-derived Netsmentioning

confidence: 99%

Reticular Chemistry 3.2: Typical Minimal Edge-Transitive Derived and Related Nets for the Design and Synthesis of Metal–Organic Frameworks

et al. 2020

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“…cluster, which can function as a hexagonal prism node for the construction of complex structures, including kce, kex, and urx topology (Figure 4). [117] Another mixed-cluster RE-MOF has been reported by Qian and co-workers. The assembly between RE 3 , RE 9 clusters, and TATB linkers leads to ZJU-16 with a 3, 6, 12-c net.…”

Section: Re-mofs Based On Re 9 Clustersmentioning

confidence: 88%

“…[ 116 ] Later, Eddaoudi and co‐workers reported a series of RE‐MOFs with different topologies based on the 12‐connected [RE 9 (μ 3 ‐OH) 12 (μ 3 ‐O) 2 (O 2 C) 12 ] cluster, which can function as a hexagonal prism node for the construction of complex structures, including kce, kex, and urx topology ( Figure ). [ 117 ] Another mixed‐cluster RE‐MOF has been reported by Qian and co‐workers. The assembly between RE 3 , RE 9 clusters, and TATB linkers leads to ZJU‐16 with a 3, 6, 12‐c net.…”

Section: Mofs Based On Y and Lns (Group 3 Metals)mentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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“…1 This approach is successfully applied for the introduction of functionality on the organic linkers and on known metal based secondary building units (SBU), 2 while structural complexity can be increased by the rational construction of new organic nodes and new nets 3 or by the synthesis of controlled multivariate materials. 4,5 Recently, design strategies have emerged that seek to deviate from this approach and attempt to increase complexity by introducing well-defined defects and mismatches into the backbone that lead to reduced symmetry, new nets and open metal sites.…”

mentioning

confidence: 99%

A Pseudo Five-Fold Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen Bonded Frameworks

Haase¹,

Craig²,

Bonneau³

et al. 2020

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Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining “incompatible” building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo C5 symmetrical organic building unit based on a pyrrole core, with a C4 symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures and topological defects in the equilibrium structure, which manifested in the formation of a hydrogen bonded framework, distorted and broken secondary building units and dangling functional groups, respectively. The influence of geometric frustration on the CO2 sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.

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Enriching the Reticular Chemistry Repertoire with Minimal Edge-Transitive Related Nets: Access to Highly Coordinated Metal–Organic Frameworks Based on Double Six-Membered Rings as Net-Coded Building Units

Cited by 52 publications

References 43 publications

Reticular Chemistry 3.2: Typical Minimal Edge-Transitive Derived and Related Nets for the Design and Synthesis of Metal–Organic Frameworks

Reticular Chemistry 3.2: Typical Minimal Edge-Transitive Derived and Related Nets for the Design and Synthesis of Metal–Organic Frameworks

Metal–Organic Frameworks Based on Group 3 and 4 Metals

A Pseudo Five-Fold Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen Bonded Frameworks

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