Reversible Redox Activity in Multicomponent Metal–Organic Frameworks Constructed from Trinuclear Copper Pyrazolate Building Blocks

Tu, Binbin; Pang, Qingqing; Xu, Huoshu; Li, Xiaomin; Wang, Yulin; Ma, Zhen; Weng, Linhong; Li, Qiaowei

doi:10.1021/jacs.7b03578

Cited by 166 publications

(122 citation statements)

References 78 publications

Supporting

Mentioning

116

Contrasting

Order By: Relevance

“…A series of MOFs with zeolitic topologies have been reported using 4,5‐imidazoledicarboxylate as a linker . In addition, different donor groups can bind to different metals to form a mixed‐metal MOF, which further diversifies the overall structure . Generally, inorganic SBUs formed by high‐valency metal ions and carboxylate‐based linkers tend to have strong stability in acidic conditions because of the low p K a of carboxylic acids.…”

Section: Stable Metal–organic Frameworkmentioning

confidence: 99%

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

et al. 2018

View full text Add to dashboard Cite

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

show abstract

Section: Stable Metal–organic Frameworkmentioning

confidence: 99%

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Multicomponent MOFs have emerging applications in catalysis, luminescence and gas storage . In order to form multicomponent MOFs judicious selection of the linkers is essential (Figure , Scheme S1) .…”

Section: Introductionmentioning

confidence: 99%

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

et al. 2020

View full text Add to dashboard Cite

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three‐dimensional cubane‐1,4‐dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB‐30), comprising cdc, 4,4′‐biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.

show abstract

“…To add further complexity, as compared to molecular solids, the construction of multicomponent MOFs in one pot requires all the components to be accommodated into a specific and preferred architecture with high openness and porosity that is consistent with a particular network topology. Previously, we have increased the structural complexity of multicomponent MOFs by producing quaternary MOFs from one metal and three linkers, and from two metals and two linkers . Recently, two examples of MOFs with one metal and four organic linkers were reported by the research groups of Zhang and Zhou in which three distinctive linkers were sequentially installed into zirconium‐based MOFs in a postsynthetic fashion.…”

Section: Figurementioning

confidence: 99%

Harnessing Bottom‐Up Self‐Assembly To Position Five Distinct Components in an Ordered Porous Framework

Diestel

Shi

et al. 2019

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

Positioning adiverse set of building blocks in awelldefined arraye nables cooperativity amongst them and the systematic programming of functional properties.T he extension of this concept to porous metal-organic frameworks (MOFs) is challenging since the installation of multiple components in aw ell-ordered framework requires careful design of the lattice topology,j udicious selection of building blocks,a nd precise control of the crystallization parameters. Herein, we report how we met these challenges to prepare the first quinary MOF structure,F DM-8, by bottom-up selfassembly from two metals,Z n II and Cu I ,a nd three distinct carboxylate-and pyrazolate-based linkers.Withasurface area of 3643 m 2 g À1 ,F DM-8 contains hierarchical pores and shows outstanding methane-storage capacity at high pressure.F urthermore,functional groups introduced on the linkers became compartmentalized in predetermined arrays in the pores of the FDM-8 framework.One distinction between synthetic materials and their natural counterparts is their level of structural complexity. Synthetic materials are typically constructed from asmall set of structural units,which places an inherent limitation on their composition and architecture.T he contrast with biological materials,such as DNAand proteins,which are composed of multiple building blocks,isstartling. Owing to acombination of structural complexity and order,s uch biomolecules are capable of sophisticated functions.W hereas conventional synthetic materials lack complexity,t he functionality of biomaterials has inspired attempts to synthesize architectures that position ab road set of building blocks in aw ell-defined array.One prominent example is the design and realization of multicomponent metal-organic frameworks (MOFs). [1] The assembly of these materials relies on the combination of multiple metal clusters and organic linkers.T hese building blocks are distinguished from one another by their coordination preferences (metals) or symmetries and metric parameters (linkers). In this way,they can be positioned in specific positions in the growing lattice,w hich mitigates against randomness and disorder. By drawing on the isoreticular principle, [2] functional groups can be placed on the organic linkers that do not interfere with framework assembly. Accordingly,specific functional groups in proximity generate precisely controlled pore environments.P ores that are programmed in this way lead to designer functions,including enhanced gas storage [3] and cooperative catalysis. [4] Theg eneration of single crystals with multiple components directly from solution becomes increasingly difficult as the number of building blocks is increased because the selfassembly process requires ac ollection of simultaneous interactions to be manipulated in ac ooperative manner.I n the case of MOFs,t he formation of alternative products is fatal, since the purification of crystalline products is virtually impossible.Todate,the number of discrete molecules that can be cocrystallized to occupy inequivalent p...

show abstract

Reversible Redox Activity in Multicomponent Metal–Organic Frameworks Constructed from Trinuclear Copper Pyrazolate Building Blocks

Cited by 166 publications

References 78 publications

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

Harnessing Bottom‐Up Self‐Assembly To Position Five Distinct Components in an Ordered Porous Framework

Contact Info

Product

Resources

About