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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Formation of Heteropolynuclear Lanthanide Complexes Using Macrocyclic Phosphonated Cyclam-Based Ligands.

Richard C Knighton1,2, Lohona K Soro2, Thibault Troadec1

  • 1Univ. Brest, UMR CNRS 6521 CEMCA, 6 Avenue Victor le Gorgeu, 29200 Brest, France.

Inorganic Chemistry
|July 9, 2020
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Summary

New pyridyl phosphonate ligands form lanthanide complexes. These ligands enable the creation of multinuclear lanthanide assemblies, with energy transfer observed between terbium and europium ions in solution.

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Area of Science:

  • Coordination Chemistry
  • Supramolecular Chemistry
  • Lanthanide Chemistry

Background:

  • Cyclam and cross-bridged cyclam scaffolds are crucial in coordination chemistry.
  • Functionalization of these scaffolds with pyridyl phosphonate groups offers unique binding properties.
  • Lanthanide complexes are vital in fields like imaging and catalysis.

Purpose of the Study:

  • To synthesize and characterize novel cyclam-based ligands (L1 and L2) functionalized with pyridyl phosphonate groups.
  • To investigate the complexation behavior of these ligands with lanthanide (Ln) cations.
  • To explore the structural, solution, and photophysical properties of the resulting lanthanide complexes and multinuclear assemblies.

Main Methods:

  • Synthesis of novel cyclam-based ligands (L1 and L2).
  • Lanthanide complexation studies using various techniques: X-ray diffraction, 1H NMR, UV-vis absorption, and luminescence spectroscopy.
  • Potentiometric and spectrophotometric titrations to investigate complex formation and multinuclear species.

Main Results:

  • Ligand L2 successfully formed octadentate 1:1 lanthanide complexes ([LnL2H]Cl or [LnL2H]), while L1 did not complex lanthanides.
  • The pyridyl phosphonate groups demonstrated the ability to chelate to a single metal center and interact with a second metal center.
  • Formation of high-order heteropolynuclear lanthanide assemblies (e.g., [TbL2]3Eu2) was observed in solution, with energy transfer between Tb and Eu.

Conclusions:

  • Novel pyridyl phosphonate functionalized cyclam ligands were synthesized and characterized.
  • Ligand L2 forms stable octadentate lanthanide complexes.
  • The ligands facilitate the construction of intricate heteropolynuclear lanthanide architectures with potential for energy transfer applications.