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Complexation Equilibria: Factors Influencing Stability of Complexes01:09

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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Protons and neutrons, collectively called nucleons, are packed together tightly in a nucleus. With a radius of about 10−15 meters, a nucleus is quite small compared to the radius of the entire atom, which is about 10−10 meters. Nuclei are extremely dense compared to bulk matter, averaging 1.8 × 1014 grams per cubic centimeter. If the earth’s density were equal to the average nuclear density, the earth’s radius would be only about 200 meters.
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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
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This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
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Structural stability and polymorphic transitions in LnSI (Ln = lanthanides).

Shohei Kawanishi1, Suguru Yoshida1, Hiroki Ubukata1

  • 1Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan. suguru.yoshida0224@gmail.com.

Dalton Transactions (Cambridge, England : 2003)
|June 19, 2025
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Lanthanide sulfide iodides exhibit unique crystal structures based on lanthanide size, transitioning from 2D to 3D forms. The cation-to-anion radius ratio unifies understanding of these diverse mixed-anion compound structures.

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Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging
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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Crystallography

Background:

  • Mixed-anion compounds display complex crystal structures due to heteroleptic coordination.
  • Lanthanide sulfide iodides (LnSI) are a class of materials with diverse structural possibilities.

Purpose of the Study:

  • Investigate the structural relationships among three polymorphs of lanthanide sulfide iodides (LnSI).
  • Understand the factors governing structural transitions in LnSI based on lanthanide size.

Main Methods:

  • Experimental synthesis and characterization of LnSI polymorphs.
  • Theoretical calculations to analyze structural relationships and phase transitions.
  • Analysis of cation-to-anion radius ratio as a descriptor for polymorphism.

Main Results:

  • Identified three distinct crystal structures for LnSI: 2D FeOCl-type (Gd-Lu), 2D SmSI-type (Pr-Sm), and 3D SrI2-type (La, Ce).
  • Observed structural transitions linked to lanthanide ionic radius and coordination number.
  • Demonstrated that the cation-to-anion radius ratio effectively predicts Ln size-dependent and pressure-induced polymorphism.

Conclusions:

  • Structural diversity in LnSI arises from lanthanide size, leading to distinct polymorphs.
  • Martensitic-like transformations involving Ln-I bond rearrangement drive structural changes.
  • The cation-to-anion radius ratio serves as a universal parameter for controlling and predicting LnSI structures.