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

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.

Publisher Summary This review is concerned with the neglected class of inorganic compounds, which contain ions of the same element in two different formal states of oxidation. Although the number of references cited in our review show that many individual examples of this class have been studied, yet they have very rarely been treated as a class, and there has never before, to our knowledge, been a systematic attempt to classify their properties in terms of their electronic and molecular structures. In the past, systems containing an element in two different states of oxidation have gone by various names, the terms “mixed valence,” nonintegral valence,” “mixed oxidation,” “oscillating valency,” and “controlled valency” being used interchangeably. Actually, none of these is completely accurate or all-embracing, but in our hope to avoid the introduction of yet another definition, we have somewhat arbitrarily adopted the phrase “mixed valence” for the description of these systems. The concept of resonance among various valence bond structures is one of the cornerstones of modern organic chemistry.

Mixed Valence Chemistry-A Survey and Classification

The General Utility Lattice Program (GULP) has been extended to include the ability to simulate polymers and surfaces, as well as adding many other new features, and the current status of the program is fully documented. Both the background theory is described, as well as providing a concise review of some of the previous applications in order to demonstrate the range of its use. Examples are presented of work performed using the new compatibilities of the software, including the calculation of Born effective charges, mechanical properties as a function of applied pressure, calculation of frequency-dependent dielectric data, surface reconstructions of calcite and the performance of a linear-scaling algorithm for bond-order potentials.

The general utility lattice program (GULP)

Although known since the late 19th century, organic–inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic–inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design

2.2. BETS Salts with Halometalate Anions 5424 3. Magnetic Metals and Semiconductors 5426 3.1. Mononuclear Metal Complexes 5427 3.1.1. Tetrahalometalates 5427 3.1.2. Hexahalo Anions 5431 3.1.3. Pseudohalide-Containing Anions 5431 3.2. Polynuclear Metal Complexes 5433 3.2.1. Dimeric Anions 5433 3.2.2. Polyoxometalate Clusters 5434 3.3. Chain Anions: Maleonitriledithiolates 5439 4. Ferromagnetic Conductors 5441 5. Ferrimagnetic Insulators 5443 6. Conclusions 5445 7. Acknowledgment 5446 8. References 5446

Magnetic Molecular Conductors

We have shown that the hexagonal layer motif [AM{sup III}(C{sub 2} O{sub 4}){sub 3}]{sup n-} containing bridging oxalate groups, which has been shown to form a wide variety of compounds with electronically inactive counter-cations having unusual cooperative magnetic properties, can also stabilize lattices containing the organic {pi}-donor BEDT-TTF. In the compounds whose structures we describe here, (BEDT-TTF){sub 4}AFe(C{sub 2}O{sub 4}){sub 3}.C{sub 6}H{sub 5} CN (A = H{sub 2}O, K, NH{sub 4}), the lattice is stabilized by C{sub 6} H{sub 5}CN molecules included in the hexagonal cavities. The packing of the BEDT-TTF in the A = K, NH{sub 4} phases is of a type not previously observed with spin-paired (BEDT-TTF){sub 2}{sup 2+} separated by closed shell (BEDT-TTF){sup 0}, while that in the superconductor is of {Beta}{double_prime} type. Both the superconducting A = H{sub 2}O and semiconducting A = K, NH{sub 4} phases contain high spin 3d{sup 5} Fe{sup III} with only very weak exchange interaction between them. Additional low temperature and high magnetic field experiments (e.g., of Schubnikov-de Haas oscillatory magnetoresistance) will be needed to delineate the Fermi surface in the superconductor. 36 refs., 11 figs., 4 tabs.

Superconducting and Semiconducting Magnetic Charge Transfer Salts: (BEDT-TTF)4AFe(C2O4)3.cntdot.C6H5CN (A = H2O, K, NH4)

The synthesis and structural and magnetic characterization of 16 compounds AMIIFeIII(C2O4)3 (A = N(n-C3H7)4, N(n-C4H9)4, N(n-C5H11)4, P(n-C4H9)4, P(C6H5)4, N(n-C4H9)3(C6H5CH2), (C6H5)3PNP(C6H5)3, As(C6H5)4; MII = Mn, Fe) are reported. X-ray powder diffraction profiles are indexed in R3c or its subgroup P6522 or P6/mmm to derive unit cell constants. The structures of all the compounds consist of two-dimensional honeycomb networks [MIIFeIII(C2O4)3-]∞. The MII = Fe compounds behave as ferrimagnets with Tc between 33 and 48 K, but five exhibit a crossover from positive to negative magnetization near 30 K when cooled in a field of 10 mT. The compounds exhibiting this unusual magnetic behavior are those that have the highest Tc. Within the set N(n-CnH2n+1)4FeIIFeIII(C2O4)3 (n = 3−5), Tc increases with interlayer separation and the low-temperature magnetization changes from positive (n = 3) to negative (n = 4, 5). In the M = MnII compounds, the in-plane cell parameter a0 is ∼0.03 A greater than in the correspond...

Ferrimagnetic Mixed-Valency and Mixed-Metal Tris(oxalato)iron(III) Compounds: Synthesis, Structure, and Magnetism.

Determining the charge distribution in BEDT-TTF salts

JD Corbett: Synthesis of solid-state materials AK Cheetham: Diffraction methods GK Wertheim: X-ray photoelectron spectroscopy and related methods WE Hatfield: Magnetic measurements RG Denning: Optical techniques CA Fyfe: High resolution solid-state MAS NMR investigations of inorganic systems CRA Catlow: Computational techniques and simulations of crystal structure A Hamnett: Transport measurements D Adams: Vibrational spectroscopy A Navrotsky: Thermodynamic aspects of inorganic solid-state chemistry

Peter Day

Papers

Magnetic Molecular Conductors

Superconducting and Semiconducting Magnetic Charge Transfer Salts: (BEDT-TTF)4AFe(C2O4)3.cntdot.C6H5CN (A = H2O, K, NH4)

Ferrimagnetic Mixed-Valency and Mixed-Metal Tris(oxalato)iron(III) Compounds: Synthesis, Structure, and Magnetism.

Determining the charge distribution in BEDT-TTF salts

Solid State Chemistry - Techniques