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Related Experiment Videos

Temperature-induced solid-state valence tautomeric interconversion in two cobalt-Schiff base diquinone complexes.

Olivier Cador1, Françoise Chabre, Andrea Dei

  • 1Laboratorio di Magnetismo Molecolare, Dipartimento di Chimica, UdR INSTM, University of Florence, Via della Lastruccia 3, 50019 Sesto Fiorentino (Firenze), Italy.

Inorganic Chemistry
|September 30, 2003
PubMed
Summary

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Cobalt and nickel complexes with terpyridine and Schiff base diquinone ligands exhibit temperature-dependent valence tautomerism. This interconversion occurs in both solution and solid states, with solid-state transitions showing higher critical temperatures.

Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Spectroscopy

Background:

  • Mixed-ligand complexes incorporating terpyridine and Schiff base diquinone ligands are of interest for their electronic properties.
  • Valence tautomerism, a change in electron distribution and spin state, is a key phenomenon in certain coordination compounds.

Purpose of the Study:

  • To synthesize and characterize novel mixed-ligand cobalt and nickel complexes with terpyridine and Schiff base diquinone ligands.
  • To investigate the temperature-dependent electronic and spectral properties, focusing on valence tautomeric interconversion.
  • To compare the behavior of these complexes in solution and in the solid state.

Main Methods:

  • Synthesis of mixed-ligand cobalt(III) and nickel(II) complexes.
  • Structural and spectroscopic characterization (e.g., electronic spectroscopy, X-ray diffraction).

Related Experiment Videos

  • Temperature-dependent studies of electronic and spectral properties in solution and solid state.
  • Electrochemical property analysis.

    • Main Results:

    • Successful preparation of [Co(III)(tpy)(Cat-N-SQ)]Y and [Ni(II)(tpy)(Cat-N-BQ)]PF(6) complexes.
    • Evidence for thermally driven valence tautomeric interconversion in the cobalt complex, from [Co(III)(tpy)(Cat-N-SQ)](+) to [Co(II)(tpy)(Cat-N-BQ)](+), involving a metal ion spin-state change.
    • The interconversion occurs in both solution and solid states, with significantly higher transition temperatures (T(c)) observed in the solid state.
    • Similar behavior was observed for a previously reported cobalt complex, [Co(III)(Cat-N-BQ)(Cat-N-SQ)].

    Conclusions:

    • The synthesized cobalt and nickel complexes exhibit distinct charge distributions and temperature-dependent electronic properties.
    • The observed valence tautomerism in cobalt complexes is influenced by temperature, solvent, and physical state (solution vs. solid).
    • The significant difference in interconversion T(c) between solid and solution states is attributed to entropy changes related to vibronic interactions.