The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.

Functional porous coordination polymers.

The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

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Engineering coordination polymers towards applications

Layered double hydroxides (LDHs) are a class of ionic lamellar compounds made up of positively charged brucite-like layers with an interlayer region containing charge compensating anions and solvation molecules. Delamination of LDHs is an interesting route for producing positively charged thin platelets with a thickness of a few atomic layers, which can be used as nanocomposites for polymers or as building units for making new designed organic-inorganic or inorganic-inorganic nanomaterials. The synthesis of nanosized LDH platelets can be generally classified into two approaches, bottom-up and top-down. It requires modification of the LDH interlamellar environment and then selection of an appropriate solvent system. In DDS intercalated LDHs, the aliphatic tails of the DDS- anions exhibit a high degree of interdigitation in order to maximize guest-guest dispersive interactions. Bellezza reported that the LDH colloids can also been obtained by employing a reverse microemulsion approach.

Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets.

The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of magnetic metal–organic frameworks, in particular those containing cobalt(II). We examine the diversity of magnetic exchange interactions between nearest-neighbour moment carriers, covering from dimers to oligomers and discuss their implications in infinite chains, layers and networks, having a variety of topologies. We progress to the different forms of short-range magnetic ordering, giving rise to single-molecule-magnets and single-chain-magnets, to long-range ordering of two- and three-dimensional networks (323 references).

Magnetic metal-organic frameworks.

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).

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

The novel binuclear hetero-metal complex, CuNi(fsacen)·3H2O, was synthesized, where H4fsacen denotes N,N′-ethylenebis(3-carboxysalicylaldimine). This complex has [CuN2O2]- and [NiO6]-chromophores and two metal ions are connected by the phenolic oxygens. The magnetic susceptibility was well explained in terms of the equation for the high-spin nickel(II)-copper(II) cluster.

A novel high-spin nickel(ii)-copper(ii) binuclear complex

A dinucleating compartmental ligand derived from the cyclic [2:1:1] condensation of 2,6-diformyl-4-methylphenol, 1,3-propanediamine, and diethylenetriamine (dien) assumes two isomeric forms in the ...

Dinuclear copper(II) complexes of a macrocyclic compartmental ligand in two isomeric forms. exogenous ion effect upon ligand isomerism

3,5-Bis(aminomethyl)pyrazole (Hbampz) forms binuclear copper(II) complexes of the formula [Cu2(bampz)2X2] (X = CI, Br). The crystal structure of [Cu2(bampz)2Br2] has been determined by the X-ray method: formula = CuBrN4C5H9, monoclinic, space group P21/n, a = 9.214(1), b = 10.078(1), c = 8.775(1) A, β = 97.33(1)°, V = 808.1 A3. Two bampz− molecules combine with two copper(II) ions via the pyrazolate nitrogen and aminonitrogen atoms in the side chains affording an essentially planar N4 environment for each metal ion. The Cu-Cu separation is 3.947(5)A. The axial site of each copper is weakly coordinated by a bromide ion with a Cu-Br distance of 2.895(4) A. Cryomagnetic investigations over the temperature range 80-300 K revealed a significant antiferromagnetic interaction through the pyrazolate bridges. The exchange integrals (J) based on the Heisenberg model (H =—2JŜ1.Ŝ2) was estimated at—200.8 and—192.0 cm−1 for [Cu2(bampz)2Cl2] and [Cu2(bampz)2Br2], respectively.

Synthesis, Structure, and Magnetic Properties of Di-μ-Pyrazolatodicopper(II) Complexes of 3,5-Bis(Aminomethyl)Pyrazole

Fluorescent spectra of the mononuclear europium(III) complex, Eu(H2 fsaen) (NO3)·5H2O, and the heteronuclear complexes MEu(fsaen) (NO3)·nH2O (n = 4 for M = Cu(II) and n = 6 for M = Ni(II)), were compared, where H4 fsaen is a binucleating ligand, N,N′-bis (3-carboxysalicylidene)ethylenediamine. It was found that the fluorescent bands of Eu(III) observed for the mononuclear complex were significantly quenched on forming binuclear complexes.

Fluorescence Quenching of Europium(III) by Heteronuclear Complex Formation with Copper(II) or Nickel(II)

The acyclic dinucleating ligand, N,N′-dimethyl-N,N′-trimethylenedi-(3-formyl-2-hydroxy-5-methylbenzylamine) (H2L), has been prepared. It combines two CuII ions with its N(amine)2O2 and O4 metal-bin...

Template Synthesis of Macrocyclic Dinuclear CuII Complexes and Conversion into Mononuclear Complexes by Site-Selective Copper Elimination.

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