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Bimacrocyclic Effect in Anion Recognition by a Copper(II) Bicyclam Complex.

Michele Invernici1, Carlo Ciarrocchi1, Daniele Dondi1

  • 1Dipartimento di Chimica, Università di Pavia, via Taramelli 12, I-27100 Pavia, Italy.

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|August 29, 2019
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Summary

The dicopper(II) complex binds anions through two distinct modes. Bridging interactions with halides and azide enhance stability, demonstrating the bimacrocyclic effect.

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Area of Science:

  • Coordination Chemistry
  • Supramolecular Chemistry
  • Inorganic Chemistry

Background:

  • Dicopper(II) complexes with bimacrocyclic ligands offer unique coordination environments.
  • Understanding anion binding modes is crucial for designing functional metal complexes.

Purpose of the Study:

  • To investigate the interaction modes of a dicopper(II) complex with various anions.
  • To elucidate the structural and thermodynamic basis for anion binding selectivity.
  • To explore the 'bimacrocyclic effect' in anion complexation.

Main Methods:

  • X-ray crystallography to determine the structure of copper-anion adducts.
  • Electron Paramagnetic Resonance (EPR) spectroscopy to detect spin-spin coupling.
  • Isothermal Titration Calorimetry (ITC) to quantify binding thermodynamics.

Main Results:

  • The dicopper(II) complex exhibits two anion interaction modes: bridging coordination and external binding.
  • Bridging coordination by halides and azide was confirmed structurally and spectroscopically.
  • Thermodynamic data revealed enhanced stability for bridging adducts, attributed to the bimacrocyclic effect.

Conclusions:

  • The bimacrocyclic ligand facilitates distinct anion binding modes in the dicopper(II) complex.
  • Simultaneous coordination of anions to both copper centers enhances complex stability.
  • This study provides insights into anion recognition and the design of multinuclear metal complexes.