Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

1. INTRODUCTION Among the classes of highly porous materials, metalÀorganic frameworks (MOFs) are unparalleled in their degree of tunability and structural diversity as well as their range of chemical and physical properties. MOFs are extended crystalline structures wherein metal cations or clusters of cations (\" nodes \") are connected by multitopic organic \" strut \" or \" linker \" ions or molecules. The variety of metal ions, organic linkers, and structural motifs affords an essentially infinite number of possible combinations. 1 Furthermore, the possibility for postsynthetic modification adds an additional dimension to the synthetic variability. 2 Coupled with the growing library of experimentally determined structures, the potential to computationally predict, with good accuracy, affinities of guests for host frameworks points to the prospect of routinely predesigning frameworks to deliver desired properties. 3,4 MOFs are often compared to zeolites for their large internal surface areas, extensive porosity, and high degree of crystallinity. Correspondingly, MOFs and zeolites have been utilized for many of the same applications

Metal–Organic Framework Materials as Chemical Sensors

Hydrogen Storage in Metal–Organic Frameworks

Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis

This review summarizes the use of metal–organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal–organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis

A family of isoreticular chiral metal−organic frameworks (CMOFs) of the primitive cubic network topology was constructed from [Zn4(μ4-O)(O2CR)6] secondary building units and systematically elongated dicarboxylate struts that are derived from chiral Mn-Salen catalytic subunits. CMOFs 1−5 were synthesized by directly incorporating three different chiral Mn-Salen struts into the frameworks under solvothermal conditions, and they were characterized by a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, and 1H NMR. Although the CMOFs 1 vs 2 and CMOFs 3 vs 4 pairs were constructed from the same building blocks, they exhibit two-fold interpenetrated or non-interpenetrated structures, respectively, depending on the steric sizes of the solvents that were used to grow the MOF crystals. For CMOF-5, only a three-fold interpenetrated structure was obtained due to the extreme length of the Mn-Salen-derived dicarboxylate strut. The open channel and pore sizes of the CMOF series vary systematical...

Isoreticular chiral metal-organic frameworks for asymmetric alkene epoxidation: tuning catalytic activity by controlling framework catenation and varying open channel sizes.

A chiral metal-organic framework for sequential asymmetric catalysis.

Blocking bimolecular activation pathways leads to different regioselectivity in metal–organic framework catalysis

Metal-organic frameworks (MOFs) are a class of organic–inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. They have received much attention in recent years owing to the ability to tune their properties for potential applications in various areas. Properly designed MOFs with uniform, periodically aligned active sites have shown great promise in catalysing shape-, size-, chemo-, regio- and stereo-selective organic transformations. This study reports the synthesis and characterization of two chiral MOFs (CMOFs 1 and 2 ) that are constructed from Mn-salen-derived dicarboxylic acids [salen is ( R , R )- N , N ′-bis(5- tert -butylsalicylidene)-1,2-cyclohexanediamine], bis(4-vinylbenzoic acid)-salen manganese(III) chloride (H 2 L 4 ) or bis(benzoic acid)-salen manganese(III) chloride (H 2 L 3 ) and [Zn 4 (μ 4 -O)(O 2 CR) 6 ] or [Zn 5 (H 2 O) 2 (μ 3 -OH) 2 (O 2 CR) 8 ] secondary building units (SBUs), respectively. The SBUs in CMOF- 1 are connected by the linear ditopic Mn-salen-derived linkers to construct a fourfold interpenetrated isoreticular MOF (IRMOF) structure with pcu topology. In CMOF- 2 , the Mn-salen centres dimerize in a cross-linking way to form a diamondoid structure with threefold interpenetration. CMOF- 1 was examined for highly regio- and stereo-selective tandem alkene epoxidation/epoxide ring-opening reactions by using the Mn-salen andZn 4 (μ 4 -O)(carboxylate) 6 active sites, respectively. Our work demonstrated the potential utility of chiral MOFs with multiple active sites in the efficient synthesis of complex molecules with excellent regio- and stereo-controls

https://royalsocietypublishing.org/doi/pdf/10.1098/rspa.2012.0100

Chiral porous metal-organic frameworks with dual active sites for sequential asymmetric catalysis

The preparation of a chiral metal-organic framework (MOF) catalyst incorporating a Mn-salen complex and its application in highly regio- and stereoselective sequential alkene epoxidation/epoxide ring-opening reactions are presented.

Feijie Song

Papers

Isoreticular chiral metal-organic frameworks for asymmetric alkene epoxidation: tuning catalytic activity by controlling framework catenation and varying open channel sizes.

A chiral metal-organic framework for sequential asymmetric catalysis.

Blocking bimolecular activation pathways leads to different regioselectivity in metal–organic framework catalysis

Chiral porous metal-organic frameworks with dual active sites for sequential asymmetric catalysis

A Chiral Metal—Organic Framework for Sequential Asymmetric Catalysis.