Metal–Organic Frameworks for Separations

Luminescent Functional Metal–Organic Frameworks

Metal–organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).

Luminescent Metal–Organic Frameworks

2.2. MOFs with Metal Active Sites 4614 2.2.1. Early Studies 4614 2.2.2. Hydrogenation Reactions 4618 2.2.3. Oxidation of Organic Substrates 4620 2.2.4. CO Oxidation to CO2 4626 2.2.5. Phototocatalysis by MOFs 4627 2.2.6. Carbonyl Cyanosilylation 4630 2.2.7. Hydrodesulfurization 4631 2.2.8. Other Reactions 4632 2.3. MOFs with Reactive Functional Groups 4634 2.4. MOFs as Host Matrices or Nanometric Reaction Cavities 4636

Engineering Metal Organic Frameworks for Heterogeneous Catalysis

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Principles Of Fluorescence Spectroscopy

Three novel metal-organic frameworks (MOFs) [Co2(C10H8N2)][C12H8O(COO)2]2, 1, [Ni2(C10H8N2)2][C12H8O(COO)2]2·H2O, 2, and [Zn2(C10H8N2)][C12H8O(COO)2]2, 3, with three-dimensional structures have been synthesized and characterized. The structures of the three compounds appear somewhat related, formed by the connectivity involving the metal polyhedra (Co4N trigonal bipyramids in 1, NiO4N2 octahedra in 2, and ZnO4 tetrahedra and ZnO3N2 trigonal bipyramids in 3), 4,4‘-oxybis(benzoate), and 4,4‘-bipyridine. The photocatalytic studies on 1−3 indicate that they are active catalysts for the degradation of orange G, rhodamine B, Remazol Brilliant Blue R and methylene blue. The compounds have also been characterized by powder X-ray diffraction, IR, thermogravitmetric analysis, UV−vis, photoluminescence, and magnetic studies.

Novel Photocatalysts for the Decomposition of Organic Dyes Based on Metal-Organic Framework Compounds

Metal–organic frameworks (MOFs) have emerged as an important family of compounds for which new properties are increasingly being found. The potential for such compounds appears to be immense, especially in catalysis, sorption and separation processes. In order to appreciate the properties and to design newer frameworks it is necessary to understand the structures from a fundamental perspective. The use of node, net and vertex symbols has helped in simplifying some of the complex MOF structures. Many MOF structures are beginning to be described as derived from inorganic structures. In this tutorial review, we have provided the basics of the node, the net and the vertex symbols and have explained some of the MOF structures. In addition, we have also attempted to provide some leads towards designing newer structures/topologies.

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Metal–organic framework structures – how closely are they related to classical inorganic structures?

Rare-earth-based metal–organic frameworks (ReMOFs) have emerged as an interesting family of compounds, for which new properties are increasingly being found. Based on the potential of ReMOFs, resulting from their optical properties, large numbers of investigations have been carried out during the last decade. Among these investigations, ReMOFs as optical sensors, using their luminescence properties, are increasingly becoming an attractive and useful topic of research. In this study, we have provided the basics of the luminescence behaviour of ReMOFs, various possible sensing mechanisms, and a summary of the uses of ReMOFs for the sensing of nitro explosives, cations, anions, small molecules, pH, and temperature.

Luminescent rare-earth-based MOFs as optical sensors

A new metal–organic framework [Co(OBA)(DATZ)0.5(H2O)] {OBA = 4,4′-oxybis(benzoic acid) and DATZ = 3,5-diamino-1,2,4-triazole}, 1, was synthesized by hydrothermal reaction. Single-crystal X-ray data of 1 confirmed two-dimensional rhombus grid network topology with a free nitrogen site of triazole ring and two amine groups of each DATZ. Photoluminescence study of 1 in aqueous medium shows blue emission at 407 nm upon excitation at 283 nm. This emissive property was used for the sensing of Al3+ ions in aqueous medium through very high luminescence turn-on (6.3-fold) along with the blue shifting (∼24 nm) of the emission peak. However, luminescence studies in the presence of other common metal ions such as Mg2+, Zn2+, Ni2+, Co2+, Mn2+, K+, Na+, Ca2+, Cd2+, Hg2+, Cu2+, Fe2+, Fe3+, and Cr3+ in aqueous medium shows luminescence quenching in varying extent. Interestingly, the luminescence turn-on-based selectivity of Al3+ ions in aqueous medium was achieved even in the presence of the highest quenchable metal ion,...

Highly Selective and Sensitive Luminescence Turn-On-Based Sensing of Al3+ Ions in Aqueous Medium Using a MOF with Free Functional Sites.

The role of temperature and time of reaction in the formation of metal−organic frameworks (MOFs) has been studied in two systems of compounds, manganese oxybis(benzoate) and manganese trimellitates, and the results compared and contrasted with other similar studies in the literature. The investigation reveals the formation of six different phases in oxybis(benzoate) and three phases in trimellitate systems. The low-temperature phases in both systems of compounds possess Mn4 cluster units linked by the carboxylate ligands, while the high-temperature phase, irrespective of the duration of the reaction, has a three-dimensional structure with −Mn−O−Mn− linkages with brucite-related layers pillared by oxybis(benzoate) and Kagome-related layers pillared by trimellitate ligands. In all of the preparation, the reactions appear to have thermodynamic control as a function of the temperature. The isolation of low-dimensional structures in manganese oxybis(benzoate) at moderate time and temperature indicates possible...

Partha Mahata

Papers

Novel Photocatalysts for the Decomposition of Organic Dyes Based on Metal-Organic Framework Compounds

Metal–organic framework structures – how closely are they related to classical inorganic structures?

Luminescent rare-earth-based MOFs as optical sensors

Highly Selective and Sensitive Luminescence Turn-On-Based Sensing of Al3+ Ions in Aqueous Medium Using a MOF with Free Functional Sites.

Role of temperature and time in the formation of infinite -M-O-M- linkages and isolated clusters in MOFs: a few illustrative examples.