Zigzag Ligands for Transversal Design in Reticular Chemistry: Unveiling New Structural Opportunities for Metal–Organic Frameworks

Guillerm, Vincent; Grancha, Thais; Imaz, Inhar; Juanhuix, Jordi; Maspoch, Daniel

doi:10.1021/jacs.8b07050

Cited by 67 publications

(77 citation statements)

References 64 publications

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“…Besides, a series of zigzag ligands have also been introduced into bcu Zr-MOFs. [181] In addition, ditopic linkers with different sizes and functional groups can be used to construct bcu Zr-MOFs. [182][183][184][185] Different structures can be obtained using ditopic V-shaped ligands.…”

Section: Zr-mofs Based On Ditopic Linkersmentioning

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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Section: Zr-mofs Based On Ditopic Linkersmentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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“…[91][92][93] However, before the advent of transversal reticular chemistry, no clear focus had been made on the potential of their unique shape ( Figure 6a). 50 By adding the transversal parameter of width (w) to the height (h) of the ligands, Guillerm et al demonstrated that, along with making ligands taller or shorter, they could also stretch them transversally, thus breaking the collinearity of the binding carboxylates. In the case of Zr-based MOFs, this effect is reflected by generation of geometry mismatch ( Figure 6b), as zigzag ligands do not match the perfect alignment of Zr clusters.…”

Section: Zigzag Ligands: Transversal Reticular Chemistrymentioning

confidence: 99%

“…32 Along these lines, scientists can employ less-symmetric organic ligands, with bend-angles, 34 introduce steric hindrance 49 or use zigzag-shaped ligands (transversal reticular chemistry). 50 These strategies all induce structural irregularity known as geometry mismatch.…”

Section: Introductionmentioning

confidence: 99%

Geometry Mismatch and Reticular Chemistry: Strategies To Assemble Metal–Organic Frameworks with Non-default Topologies

2019

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The past 20 years have witnessed tremendous advances in the field of porous materials, including the development of novel metal-organic frameworks (MOFs) that show great potential for practical applications aimed at addressing global environmental and industrial challenges. A critical tool enabling this progress has been reticular chemistry, through which researchers can design materials that exhibit highly regular (i.e. edge-transitive) topologies, based on the assembly of geometrically-matched building blocks into specific nets. However, innovation sometimes demands that researchers steer away from default topologies to instead pursue unusual geometries. In this review, we cover this aspect and introduce the concept of geometry mismatch, in which seemingly incompatible building blocks are combined to generate non-default structures. We describe diverse MOF assemblies built through geometry mismatch generated by use of ligand bend-angles, twisted functional groups, zigzag ligands and other elements, focusing on carboxylate-based MOFs combined with common inorganic clusters. We aim to provide a fresh perspective on rational design of MOFs and to help readers understand the countless options now available to achieve greater structural complexity in MOFs.

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“…Notably, the combination of hexanuclear MBBs with tetratopic ligands may result in an excess of 10 unique nets depending on node connectivity and various conformational properties . Where such parameters may be systematically controlled, the practice of isoreticular chemistry allows further opportunities to tune material properties such as the defects concentration, as seen in a recent example illustrating the use of transversal design in Zr‐MOFs by Guillerm et al Nevertheless, the synthetic effort involved in precise manipulation of these parameters may be significant, yet conflict with other attempts to introduce nonstructural functional moieties.…”

Section: Reticular Chemistry Of Mofsmentioning

confidence: 99%

Atomic‐ and Molecular‐Level Design of Functional Metal–Organic Frameworks (MOFs) and Derivatives for Energy and Environmental Applications

et al. 2019

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Continuing population growth and accelerated fossil‐fuel consumption with recent technological advancements have engendered energy and environmental concerns, urging researchers to develop advanced functional materials to overcome the associated problems. Metal–organic frameworks (MOFs) have emerged as frontier materials due to their unique porous organic–inorganic hybrid periodic assembly and exceptional diversity in structural properties and chemical functionalities. In particular, the modular nature and modularity‐dependent activity of MOFs and MOF derivatives have accentuated the delicate atomic‐ and molecular design and synthesis of MOFs, and their meticulous conversion into carbons and transition‐metal‐based materials. Synthetic control over framework architecture, content, and reactivity has led to unprecedented merits relevant to various energy and environmental applications. Herein, an overview of the atomic‐ and molecular‐design strategies of MOFs to realize application‐targeted properties is provided. Recent progress on the development of MOFs and MOF derivatives based on these strategies, along with their performance, is summarized with a special emphasis on design–structure and functionality–activity relationships. Next, the respective energy‐ and environmental‐related applications of catalysis and energy storage, as well as gas storage‐separation and water harvesting with close association to the energy–water–environment nexus are highlighted. Last, perspectives on current challenges and recommendations for further development of MOF‐based materials are also discussed.

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Zigzag Ligands for Transversal Design in Reticular Chemistry: Unveiling New Structural Opportunities for Metal–Organic Frameworks

Cited by 67 publications

References 64 publications

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Geometry Mismatch and Reticular Chemistry: Strategies To Assemble Metal–Organic Frameworks with Non-default Topologies

Atomic‐ and Molecular‐Level Design of Functional Metal–Organic Frameworks (MOFs) and Derivatives for Energy and Environmental Applications

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