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.

Layered double hydroxides (LDHs) have been known for a considerable time and have been widely studied. The basic features of their structure, involving positively charged brucite-like layers together with charge-balancing anions and water in interlayer galleries are well understood, but some detailed aspects of their structure have been the subject of controversy in the literature. In this article we review the wide range of experimental and theoretical studies of the structure of LDHs, highlighting areas of consensus and currently unresolved issues. We focus on the range of composition for which LDHs may be formed, possible layer stacking polytypes, arrangement of guest species in the interlayer galleries and the extent of order-disorder phenomena, both long-range and short-range, in the layers and interlayer galleries.

Structural aspects of layered double hydroxides

Pressure induced amorphization of materials

▪ Abstract The mechanisms of exchange of hydrogen between the deep interior and surface of Earth, as well as the means of retention and possible abundance of hydrogen deep within the Earth, are examined. The uppermost several hundred kilometers of Earth's suboceanic upper mantle appear to be largely degassed, but significant primordial hydrogen could be retained within the transition zone, lower mantle, or core. Regassing of the planet occurs via subduction: Cold slabs are likely particularly efficient at transporting hydrogen to depth within the planet. Marked changes in hydrogen cycling have taken place throughout Earth's history: Evidence of hydrated ultramafic melts in the Archean and probable hydrogen retention within a Hadean magma ocean indicate that early in its history, the deep Earth was substantially wetter. The largest enigma associated with hydrogen in the deep Earth lies in the core: This region could represent the dominant reservoir of hydrogen on the planet, with up to ∼100 hydrospheres of...

https://www.eoas.ubc.ca/~mjelline/453website/eosc453/E_prints/AnnRev.29.1.365.pdf

Hydrogen in the Deep Earth

Neutron diffraction data suitable for Rietveld refinements were collected on a powder sample of synthetic Mg(OH)2 by the Polaris time-of-flight spectrometer (ISIS spallation source, U.K.) at 10-4 7.8(3) and 10.9(6) GPa. The Paris-Edinburgh high-pressure cell with WC anvils was used. Pressure calibration and equation-ofstate results were attained by separate runs with an NaCl internal standard. Interpolation of p(V) data by the fourth-order Birch-Murnaghan e.o.s. yields K
0=41(2) GPa, K′0=4(2) and K″0=1.1(9) GPa-1. The bulk modulus obtained is smaller than previously reported results. Rietveld refinements (R

 prof
 =1.45% and 2.02% at 10-4 and 10.9 GPa) show that H lies on the threefold axis (1/3, 2/3, z) up to 10.9 GPa, where a model with H disordered in (x, 2x, z) can be refined. In the latter case, a hydrogen bond with O-H=0.902(7), H..O′=2.026(8) A and <OHO′=145.9 (7)° is observed. Differences with previous results for deuterated brucite are discussed. The onset of H disorder, and a jump of the c/a ratio vs. pressure at 6–7 GPa, may be related to a second-order phase transition consistent with recently reported Raman spectroscopic results.

Robert B. Von Dreele

Papers

Pressure-induced H bonding; neutron diffraction study of brucite, Mg(OD) 2 , to 9.3 GPa