http://pubs.acs.org/doi/pdf/10.1021/cr300014x

Introduction to Metal–Organic Frameworks

/pdf/metal-organic-frameworks-and-self-assembled-supramolecular-2xs948xxr9.pdf

Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

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.

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

Ferroelectric Metal–Organic Frameworks

Constructing magnetic molecular solids by employing three-atom ligands as bridges

The study of paramagnetic compounds based on 4d and 5d transition metals is an emerging research topic in the field of molecular magnetism. An essential driving force for the interest in this area is the fact that heavier metal ions introduce important attributes to the physical properties of paramagnetic compounds. Among the attractive characteristics of heavier elements vis-a-vis magnetism are the diffuse nature of their d orbitals, their strong magnetic anisotropy owing to enhanced spin–orbit coupling, and their diverse structural and redox properties. This critical review is intended to introduce readers to the topic and to report recent progress in this area. It is not fully comprehensive in scope although we strived to include all relevant topics and a large subset of references in the area. Herein we provide a survey of the history and current status of research that has been conducted on the topic of second and third row transition metal molecular magnetism. The article is organized according to the nature of the precursor building blocks with special topics being highlighted as illustrations of the special role of heavier transition metal ions in the field. This paper is addressed to readers who are interested in molecular magnetism and the application of coordination chemistry principles to materials synthesis (231 references).

Molecular magnetic materials based on 4d and 5d transition metals.

Three isomorphous compounds M(CHOO)3[NH2(CH3)2] (M = Mn(1·Mn), Co(2·Co), Ni(3·Ni)) have been synthesized in solvothermal conditions. Single-crystal X-ray diffraction shows that they are all crystallized in the trigonal space group R 3c with small differences in the lattice parameters. Bridged by the three-atom single-bridge CHOO-, M ions form a three-dimensional distorted perovskite-like structure with dimethylamine (DMA) cations located in the cages of the network. Based on the magnetic data, these three 3D compounds are weak ferromagnets with the critical temperature Tc = 8.5 K (1·Mn), 14.9 K (2·Co), and 35.6 K (3·Ni), and for 2·Co and 3·Ni, spin reorientation might take place at 13.1 and 14.3 K, respectively. At 1.8 K, hysteresis loops can be observed for all three compounds with the coercivity field ca. 90 Oe (1·Mn), 920 Oe (2·Co), and 320 Oe (3·Ni). The canting angles are estimated to be 0.08°, 0.5°, and 0.6° for 1·Mn, 2·Co, and 3·Ni, respectively. The magnetic coupling between MnII ions in 1·Mn was...

Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials

Three azido-bridged Co2+ complexes with square, honeycomb, and Kagome layered structures were synthesized and structurally characterized. Crystallization solvents are found to be critical in generating the observed topologies. These structurally related complexes are of significance in studying two-dimensional antiferromagnetism and geometric frustration.

Solvent-tuned azido-bridged Co2+ layers: square, honeycomb, and Kagomé.

Two novel three-dimensional complexes formulated as [M3(bime)2(μ3-OH)2(HO−BDC)2]n (M = Co, 1; Cu, 2) [bime = 1,2-bis(imidazol-1‘-yl)ethane, HO−H2BDC = 5-hydroxyisophthalic acid] have been hydrothermally synthesized and characterized Both 1 and 2 exhibit similar structural frameworks resulting from one-dimensional metal/oxygen chains extended by HO−BDC, but the bridging modes of HO−BDC and coordination environments of metal centers are different Complexes 1 and 2 crystallize in the orthorhombic system, space group Pbcn, a = 18458(2) [182119(12) for 2] A, b = 120616(14) [116847(7)] A, c = 114859(14) [120688(6)] A, and Z = 4 (4) Magnetic studies show that 1 displays a slow magnetic relaxation, a large hysteresis, and distinct finite-size effects and 2 contains an antiferromagnetic chain

Two Three-Dimensional Metal−Organic Frameworks Containing One-Dimensional Hydroxyl/Carboxylate Mixed Bridged Metal Chains: Syntheses, Crystal Structures, and Magnetic Properties

Xin-Yi Wang

Papers

Constructing magnetic molecular solids by employing three-atom ligands as bridges

Molecular magnetic materials based on 4d and 5d transition metals.

Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials

Solvent-tuned azido-bridged Co2+ layers: square, honeycomb, and Kagomé.

Two Three-Dimensional Metal−Organic Frameworks Containing One-Dimensional Hydroxyl/Carboxylate Mixed Bridged Metal Chains: Syntheses, Crystal Structures, and Magnetic Properties