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Electronic Structure Modulation in an Exceptionally Stable Non-Heme Nitrosyl Iron(II) Spin-Crossover Complex
Lucía Piñeiro-López1, Norma Ortega-Villar2, M Carmen Muñoz3
1Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, 46980 Paterna, Valencia, Spain.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 16, 2016
Summary
This study details a stable iron complex exhibiting spin crossover behavior due to magnetic coupling between the NO radical and iron spin states. Structural analysis reveals how electronic distribution influences the {FeNO}(7) bond across a wide temperature range.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Magnetochemistry
Background:
- Nitrosyl iron complexes are crucial in understanding spin crossover (SCO) phenomena.
- The interplay between electronic states and structural changes in SCO materials is key to their applications.
Purpose of the Study:
- To synthesize and characterize a stable nitrosyl iron(II) mononuclear complex with SCO behavior.
- To investigate the temperature-dependent crystal structure and its correlation with magnetic properties.
- To elucidate the electronic factors governing the {FeNO}(7) bond and SCO mechanism.
Main Methods:
- Synthesis of the [Fe(bztpen)(NO)](PF6 )2 complex.
- Variable-temperature (120-420 K) single-crystal X-ray diffraction.
- Magnetic susceptibility measurements.
- Density Functional Theory (DFT) calculations.
Main Results:
- The complex exhibits a robust S=1/2↔S=3/2 spin crossover at 370 K.
- Detailed crystal structures reveal temperature-dependent changes in the {FeNO}(7) bond and {FeNO}(7) bond.
- Magneto-structural correlations demonstrate the influence of t2g -eg orbital electronic distribution on SCO.
Conclusions:
- The studied iron complex displays significant spin crossover behavior driven by strong magnetic coupling.
- Variable-temperature structural data provides insights into the mechanism of SCO in nitrosyl iron complexes.
- The findings offer valuable correlations between electronic structure, magnetic properties, and molecular geometry.
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