This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

/pdf/secondary-building-units-nets-and-bonding-in-the-chemistry-o0m4ttzsgz.pdf

Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

2.1.2. Low Topology/Framework Density 1003 2.1.3. Side Group Directed Superstructures 1003 2.2. Synthesis Considerations 1003 2.3. Special Properties 1004 3. Metal Imidazolate Frameworks 1004 3.1. Chains and Rings 1004 3.2. Zeolitic and Zeolite-like Frameworks 1006 3.2.1. SOD-Type Zinc(II) 2-Methylimidazolate 1007 3.3. Nonporous 4-Connected Networks 1010 3.4. Polyimidazolates 1011 4. Metal Pyrazolate Frameworks 1011 4.1. Clusters and Chains 1011 4.2. 3D Networks Based on Polypyrazolates 1012 5. Metal 1,2,4-Triazolate Frameworks 1014 5.1. Simple 3-Connected Networks 1015 5.2. Quasi-Imidazolates 1018 5.3. With Coordinative Substituents 1019 5.4. With Secondary Counterions and/or Ligands 1021 6. Metal 1,2,3-Triazolate Frameworks 1023 7. Metal Tetrazolate Frameworks 1025 7.1. Univalent Coinage-Metal Tetrazolate Frameworks 1025

Metal Azolate Frameworks: From Crystal Engineering to Functional Materials

Coordination complexes exhibiting room-temperature phosphorescence: Evaluation of their suitability as triplet emitters in organic light emitting diodes

Applications of Supramolecular Anion Recognition

After three decades of intense and fundamental research on metal–organic frameworks (MOFs), is there anything left to say or to explain? The synthesis and properties of MOFs have already been comprehensively described elsewhere. It is time, however, to prove the nature of their true usability: technological applications based on these extended materials require development and implementation as a natural consequence of the up-to-known intensive research focused on their design and preparation. The current large number of reviews on MOFs emphasizes practical strategies to develop novel networks with varied crystal size, shape and topology, being mainly devoted to academic concerns. The present survey intends to push the boundaries and summarise the state-of-the-art on the preparation of promising (multi)functional MOFs in worldwide laboratories and their use as materials for industrial implementation. This review starts, on the one hand, to describe several tools and striking examples of remarkable and recent (multi)functional MOFs exhibiting outstanding properties (e.g., in gas adsorption and separation, selective sorption of harmful compounds, heterogeneous catalysis, luminescent and corrosion protectants). On the other hand, and in a second part, it intends to use these examples of MOFs to incite scientists to move towards the transference of knowledge from the laboratories to the industry. Within this context, we exhaustively review the many efforts of several worldwide commercial companies to bring functional MOFs towards the daily use, analysing the various patents and applications reported to date. Overall, this review goes from the very basic concepts of functional MOF engineering and preparation ending up in their industrial production on a large scale and direct applications in society.

/pdf/multifunctional-metal-organic-frameworks-from-academia-to-b8ttedwosv.pdf

Multifunctional metal–organic frameworks: from academia to industrial applications

Structural and functional evolution of metallacrowns.

Anion Encapsulation by Neutral Supramolecular Assemblies of Cyclic CuII Complexes: A Series of Five Polymerization Isomers, [{cis‐CuII(μ‐OH)(μ‐pz)}n], n=6, 8, 9, 12, and 14

Magnetic susceptibility and EPR studies show that trinuclear Cu II pyrazolato complexes with a Cu3(I3-X)2 core (X ) Cl, Br) are ferromagnetically coupled: JCu-Cu ) +286 cm -1 (X ) Cl), +31 cm -1 (X ) Br) The orderly transition from an antiferromagnetic to a ferromagnetic exchange among the Cu centers of Cu3(I3-X) complexes, X ) O, OH, Cl, Br, follows the change of the CuX-Cu angle from 120° to 80° The crystal structures of [Bu4N]2[Cu3(I3-Br)2(I-pz*)3Br3] (pz* ) pz (1a )o r 4-O 2N-pz (1b), pz ) pyrazolato anion, C3H3N2 1- ) are presented

Triangular, ferromagnetically-coupled CuII 3-pyrazolato complexes as possible models of particulate methane monooxygenase (pMMO).

Misapplication of chemical water treatment inhibition technologies results in the formation of water-formed scale deposits (notably, CaCO3 and BaSO4) that interfere with proper system operation. These are removed by chemical additives through dissolution. Herein, we report the efficient dissolution of CaCO3 at pH 4 by 2-phosphonobutane-1,2,4-tricarboxylic acid (H5PBTC). We also report the identity of the Ca-containing dissolution product, characterized by single-crystal X-ray crystallography and a variety of spectroscopic techniques, as (Ca(H3PBTC)(H2O)2‚2H2O)n. It is the first metal -PBTC complex reported to date. In the structure of polymeric (Ca(H3- PBTC)(H2O)2‚2H2O)n Ca 2+ is seven-coordinated, bound by two phosphonate oxygens, three carboxylate oxygens, and two water molecules. (Ca(H3PBTC)(H2O)2‚2H2O)n was also prepared by designed synthesis by reacting various Ca 2+ sources and H5PBTC. Studies of anticorrosion properties of Ca2+/H3PBTC2- combinations are also reported. Organic phosphonates are used extensively in a plethora of technological applications. 1 In medical and pharmaceutical applica- tions, organic phosphonates are used extensively as regulators of calcium phosphate metabolism 2 and for treatment of calcium deposition diseases.3 Industrial applications include chemical water treatment, 4 dispersion technology, 5 and metallic corrosion control. 6

/pdf/phosphonopolycarboxylates-as-chemical-additives-for-calcite-4qzrlhftov.pdf

Phosphonopolycarboxylates as Chemical Additives for Calcite Scale Dissolution and Metallic Corrosion Inhibition Based on a Calcium-Phosphonotricarboxylate Organic-Inorganic Hybrid

Gellert Mezei

Papers

Structural and functional evolution of metallacrowns.

Anion Encapsulation by Neutral Supramolecular Assemblies of Cyclic CuII Complexes: A Series of Five Polymerization Isomers, [{cis‐CuII(μ‐OH)(μ‐pz)}n], n=6, 8, 9, 12, and 14

Triangular, ferromagnetically-coupled CuII 3-pyrazolato complexes as possible models of particulate methane monooxygenase (pMMO).

Phosphonopolycarboxylates as Chemical Additives for Calcite Scale Dissolution and Metallic Corrosion Inhibition Based on a Calcium-Phosphonotricarboxylate Organic-Inorganic Hybrid

Effect of copper-substitution on the structure and nuclearity of Cu(II)-pyrazolates: from trinuclear to tetra-, hexa- and polynuclear complexes