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Ionic Radii03:10

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Ionic radius is the measure used to describe the size of an ion. A cation always has fewer electrons and the same number of protons as the parent atom; it is smaller than the atom from which it is derived. For example, the covalent radius of an aluminum atom (1s22s22p63s23p1) is 118 pm, whereas the ionic radius of an Al3+ (1s22s22p6) is 68 pm. As electrons are removed from the outer valence shell, the remaining core electrons occupying smaller shells experience a greater effective nuclear...
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When atoms gain or lose electrons to achieve a more stable electron configuration they form ions. Ionic bonds are electrostatic attractions between ions with opposite charges. Ionic compounds are rigid and brittle when solid and may dissociate into their constituent ions in water. Covalent compounds, by contrast, remain intact unless a chemical reaction breaks them.
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Solubility is the measure of the maximum amount of solute that can be dissolved in a given quantity of solvent at a given temperature and pressure. Solubility is usually measured in molarity (M) or moles per liter (mol/L). A compound is termed soluble if it dissolves in water.
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Crystalline solids are divided into four types: molecular, ionic, metallic, and covalent network based on the type of constituent units and their interparticle interactions.
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An element composed of atoms that readily lose electrons (a metal) can react with an element composed of atoms that readily gain electrons (a nonmetal) to produce ions through complete electron transfer. The compound formed by this transfer is stabilized by the electrostatic attractions (ionic bonds) between the oppositely charged ions.
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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates.

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New luminescent ionic liquids featuring lanthanide saccharinate anions were synthesized. These materials exhibit tunable luminescence properties, with potential applications in lighting and sensing technologies.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Luminescent Materials

Background:

  • Ionic liquids (ILs) are versatile solvents and materials with unique properties.
  • Lanthanide complexes are known for their characteristic luminescence.
  • Saccharinate anions offer potential for designing novel coordination compounds.

Purpose of the Study:

  • To synthesize and characterize novel luminescent ionic liquids incorporating complex lanthanide saccharinate anions.
  • To investigate the structural, thermal, and photoluminescent properties of these new materials.
  • To explore the influence of coordination environment and ligands on luminescence efficiency and decay times.

Main Methods:

  • Synthesis of ionic liquids: 1-butyl-3-methylimidazolium saccharinate ([C4mim][Sac]) and N-butyl-4-methylpyridinium saccharinate ([C4mpy][Sac]).
  • Reaction of ionic liquids with lanthanide saccharinates to form target compounds.
  • Single-crystal X-ray diffraction for structural determination.
  • Differential scanning calorimetry (DSC) for thermal analysis.
  • Photoluminescence spectroscopy (excitation, emission, decay time measurements) to evaluate luminescence properties.

Main Results:

  • Four luminescent ionic liquids with complex lanthanide saccharinate anions were successfully synthesized: [C4mim]3[Eu(Sac)6(H2O)2] (1), {C4mpy}5{[Ln(Sac)6(H2O)2][Ln(Sac)5(H2O)3]}{(H2O)2(CH3CN)2} (Ln = Sm for 2a; Eu for 2b), and [C4mpy]3[Eu(Sac)6][CH3CN] (3).
  • Structural analysis revealed varying coordination numbers (6 or 8) for lanthanide centers, influenced by the presence of saccharinate anions and aqua ligands.
  • Compounds 1, 2b, and 3 exhibited characteristic red emission of Eu(III) with significantly enhanced quantum efficiencies for compound 3 (57.75%) compared to 1 (15.9%) and 2b (22.95%), attributed to the absence of aqua ligands in its coordination sphere.
  • Compound 2a showed characteristic Sm(III) emission in the orange-red region.
  • Thermal analysis indicated that compound 1 is an ionic liquid, while 2 and 3 are low-temperature molten salts.

Conclusions:

  • Novel luminescent ionic liquids and molten salts containing lanthanide saccharinate anions have been developed.
  • The luminescence properties, particularly quantum efficiency and decay time, are strongly influenced by the coordination environment around the lanthanide ion, with anhydrous complexes showing superior performance.
  • These materials demonstrate potential for applications requiring efficient red and orange-red light emission.