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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.
Dalton Transactions (Cambridge, England : 2003)
|January 31, 2017
Summary
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.
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.
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