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A luminescent Pt2Fe spin crossover complex.

Bernhard Schäfer1, Thomas Bauer2, Isabelle Faus2

  • 1Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. Mario.Ruben@kit.edu.

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Summary
This summary is machine-generated.

A new heterotrinuclear platinum-iron spin crossover complex exhibits reversible spin switching in one crystalline form (1L) but not the other (1H), with potential for light-induced spin state switching.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Magnetochemistry

Background:

  • Spin crossover (SCO) complexes are molecular materials exhibiting switchable magnetic properties.
  • Developing heterometallic SCO complexes offers tunable properties and novel functionalities.
  • Understanding structure-property relationships is crucial for designing advanced SCO materials.

Purpose of the Study:

  • To synthesize and characterize a novel heterotrinuclear [Pt2Fe] SCO complex.
  • To investigate the influence of crystal packing and solvent molecules on SCO behavior.
  • To explore the magnetic, vibrational, and photophysical properties of the synthesized complex.

Main Methods:

  • Synthesis of the [Pt2Fe] SCO complex using a ditopic bridging bpp-alkynyl ligand.
  • X-ray crystallography to determine crystal structures (1H and 1L) and solvent content.
  • Temperature-dependent magnetic susceptibility and Mössbauer spectroscopy to study SCO.
  • Experimental nuclear resonance vibrational spectroscopy (NRVS) and DFT calculations for vibrational analysis.
  • Transient absorption spectroscopy to investigate photophysical properties and energy transfer pathways.

Main Results:

  • Two distinct crystalline forms (1H and 1L) of the [Pt2Fe] complex were identified, differing in molecular packing and solvent content.
  • The 1L form displayed reversible SCO behavior with a transition temperature of 268 K, while the 1H form remained in the high-spin state.
  • 1L was found to be excitable to a light-induced excited spin-state trapping (LIESST) state.
  • Vibrational properties were analyzed using NRVS and DFT, assigning modes to specific components.
  • Photophysical studies revealed potential energy transfer from photoexcited Pt(II) units to the Fe(II) moiety in solution.

Conclusions:

  • Crystal packing and solvent molecules significantly impact the SCO properties of the [Pt2Fe] complex.
  • The synthesized complex demonstrates tunable SCO behavior and potential for light-driven spin manipulation.
  • The study provides insights into the interplay between structural, magnetic, vibrational, and photophysical properties in heterometallic SCO systems.