Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.

Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations

Metal-organic frameworks based upon non-zeotype 4-connected topology

A mechanistic approach towards the photocatalytic organic transformations over functionalised metal organic frameworks: a review

Three new metal–organic frameworks (MOFs) of Co(II), [{Co(muco)(bpa)(2H2O)}·2H2O]n (1), [{Co(muco)(azopy)}·H2O]n (2), and [{Co(muco)(4bpdp)}·2DMF·H2O]n (3) (where, muco = trans, trans-muconate dianion, bpa = 1,2-bis(4-pyridyl)ethane, azopy = 4,4′-bisazobipyridine, and 4bpdb = 1,4- bis(4-pyridyl)-2,3-diaza-1,3-butadiene) have been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. Structural analysis revealed that MOF1 exhibits an interesting 3-fold interpenetrated three-dimensional (3D) pillar-layered framework structure with 4-c, {66} topology, while 2 and 3 possess a 2-fold interpenetrated 3D pillar-layered framework structure with 7-c, {3∧3.4∧13.5∧4.6} net topology. Gas adsorption study of the compounds shows that 1 exhibits selective adsorption of CO2 over other (H2, N2, and Ar) gases with an uptake higher than those of 2 and 3. Further, the metal coordinated water molecules in MOF1 can be reversibly removed by high temperature treatment to generate a dehydrated f...

Interpenetrated Metal–Organic Frameworks of Cobalt(II): Structural Diversity, Selective Capture, and Conversion of CO2

Four new heterometallic coordination complexes, namely, {[Zn4Ln2(imdc)4(SO4)(H2O)8]·4H2O}n [Ln = Nd (1), Sm (2), Eu (3), Gd (4); H3imdc = imidazole-4,5-dicarboxylic acid], were hydrothermally synthesized by the reactions of Ln2O3 with imidazole-4,5-dicarboxylic acid and ZnSO4·7H2O and characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). The single-crystal X-ray diffraction analyses reveal that these polymers are isostructural and possess an interesting 3D pillar-layered architecture with 424·64 topology, in which 2D layers constructed by alternately arranged 1D right-/left-handed helical chains of [Zn2(μ5-imdc)]n bridged via dimeric Eu2 units are pillared by μ2-SO42− and μ3-imdc3− anions. The liquid fluorescence of compounds 1–3 at room temperature shows that these complexes are very good chemosensors for I− ion, and the response of the sensor is based on fluorescence quenching of Zn–Ln MOFs by iodine ions.

Construction of four 3d–4f heterometallic pillar-layered frameworks containing left- and right-handed helical chains and a I− chemosensor

Presented here is a chiral three-dimensional indium(III)-organic compound [In(5-Aip)2]·(TPP)·4H2O (1; 5-Aip = 5-aminoisophthalate, TPP = tetraphenylphosphonium). The structure of 1 features an unusual tetrahedral anionic framework containing tetrahedral TPP guests. This compound shows interesting photoluminescent properties and notable catalytic activity on the diethylzinc addition to benzaldehyde. The results reveal that the employment of tetrahedral TPP cations as guests can not only direct the formation of a tetrahedral framework but also help on the improvement of physical properties.

Yun-Cui Ma

Papers

A Chiral Tetrahedral Framework with Tetrahedral Guests for Catalysis and Photoluminescence

An effective approach for constructing acentric heterometallic-organic framework with catalytic activity

Oat-Soybean Rotation Mechanized Production for Efficient Industrial Crop Use of Saline Land: Evidence from the Yellow River Delta, China