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Solvent-Induced Spin-State Change in Copper Corroles.

Christopher M Lemon1,2, Andrew G Maher1, Bryce L Anderson1

  • 1Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts02138, United States.

Inorganic Chemistry
|December 2, 2022
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Summary
This summary is machine-generated.

Copper corroles in coordinating solvents change from a radical cation to a triplet state, then reduce. This explains solvent-induced paramagnetism and color changes in copper corrole chemistry.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Photochemistry

Background:

  • The electronic structure of copper corroles has been debated.
  • Copper corroles exhibit paramagnetism and color changes in coordinating solvents, with unknown underlying chemistry.

Purpose of the Study:

  • To elucidate the solvent-induced changes in the electronic structure and properties of copper corroles.
  • To explain the observed paramagnetism and color changes in coordinating solvents.

Main Methods:

  • Spectroscopic analysis
  • Computational modeling
  • Kinetic studies

Main Results:

  • Coordinating solvents like pyridine induce a spin state change from an antiferromagnetic Cu(II) corrole radical cation to a ferromagnetic triplet state.
  • The triplet state undergoes further reaction over time, yielding a one-electron-reduced Cu(II) corrole species.
  • These transformations explain the observed solvent-induced paramagnetism and color shifts.

Conclusions:

  • The study reveals the dynamic electronic structure changes in copper corroles driven by coordinating solvents.
  • The findings provide a chemical basis for understanding solvent effects on copper corrole properties.
  • This work clarifies long-standing questions regarding copper corrole behavior in solution.