The enthalpies for formation of five Eu3+ complexes with N-piperidinomethane-1,1-diphosphonic acid (H4pmdp) have been determined by titration calorimetry in 2 M (Na,H)ClO4 media at 25 °C Both protonation enthalpies and entropies, and the structure of H4pmdp in the solid state indicate protonation of the piperidine nitrogen to give a zwitterion in the free ligand Luminescent lifetime measurements show that the formation of the 1∶1 and 1∶2 Eu∶L complexes of a variety of methane-1,1-diphosphonic acids liberates an average of 33 ± 01 water molecules per ligand from the Eu inner hydration sphere The number of water molecules in the inner coordination sphere and the thermodynamic parameters of the complexes suggest that the structure of the Eu3+–pmdp complexes and the strength of the Eu3+–pmdp bonds are similar to those of other methane-1,1-diphosphonic acids despite the presence of the piperidine ring However, the complexation entropies argue for weaker solvation of the Eu–pmdp complexes probably due to the hydrophobic character of the piperidine ring

Thermodynamics and hydration of the europium complexes of a nitrogen heterocycle methane-1,1-diphosphonic acid

Metal alkanoates combine simple chemical structures and a versatility of condensed states of matter they exhibit. Solid crystals, plastic crystals, lyotropic and thermotropic ionic liquid crystals, liquids, mesomorphic glasses, and Langmuir–Blodgett films are just a few examples. Liquid crystal phases of metal alkanoates are the most intriguing because they represent a non-conventional class of materials known as ionic metallomesogens. Structural, thermal, and transport properties of mesomorphic metal alkanoates are well documented and reviewed. On the contrary, the optical and nonlinear-optical properties of these materials are very poorly understood. The situation has changed rapidly during the last decade. Advances in the design of mesomorphic glasses stable at room temperatures have launched a new era of research in the field of photonic and optoelectronic materials based on mesomorphic metal alkanoates. This manuscript reviews recent developments in the field of optical and nonlinear-optical material...

Versatile nonlinear-optical materials based on mesomorphic metal alkanoates: design, properties, and applications

In nature, the elements of the inorganic part of the periodic table are found in three forms: metals, ions in salts & minerals, and ions in solution. The ions may be coordinated to simple or complicated ligands. They may form purely electrostatic or partially covalent bonds. A common trend is that the more covalent bonds an element form, the more we know of its physicochemical properties. The rare earths form purely electrostatic bonds, thus, our understanding of the solution chemistry of these elements is limited-yet important. Most rare earth elements used today pass through hydrometallurgical processes that rely on the solution chemistry of these elements, even through the critical applications are in alloys and functional materials. Through developments in optical spectroscopy, total X-ray scattering, and quantum chemical methods we are posed to remedy this situation: we are ready to create predictive structure-property relationships in the field of lanthanide solution chemistry. The scope of this review is to summarise the state-of-the-art for neodymium(III), to go through the structure-property relationships that are in use. In the form of NdFeB magnets, neodymium plays a crucial role in green energy production and electric propulsion. As a 4f3 ion in solution it is also one of the simpler rare earth ions, and the Nd(III) ion has characteristic optical properties that can be exploited as a handle in physicochemical studies. Here, we start with a critical review of the current concepts used to relate structure and electronic energy levels. We follow with our suggested approach of using the methodology from molecular photophysics to relate optical properties and structure, and conclude with selected literature examples.

Optical spectroscopy as a tool for studying the solution chemistry of neodymium(III).

Bisphosphonates: synthesis, structures, properties, medical and industrial applications

For decades Judd–Ofelt (JO) theory has been used for describing the intensity of f ↔ f transitions in lanthanides. Theory has proved to be a very useful tool for radiative lifetimes calculation, branching ratios and radiative transitions probability estimation. In this paper, Judd–Ofelt theory is used to simulate the absorption spectrum of Nd3+-doped fluoroaluminate glass. The presented procedure is considered as a tool to determine JO parametrization quality and to estimate linewidths.

Simulation of the absorption spectrum of Nd3+ activated fluoroaluminate glass

Spectroscopic study of neodymium soaps in 1-pentanol

Spectroscopic analysis of the complexes of the Eu3+ ion with 1-hydroxyethane-1,1-diphosphonic acid in the solid state and in a 2 M NaNO3 solution

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Spectroscopic study of neodymium soaps in 1-pentanol

Spectroscopic analysis of the complexes of the Eu3+ ion with 1-hydroxyethane-1,1-diphosphonic acid in the solid state and in a 2 M NaNO3 solution