Hysteretic spin crossover driven by anion conformational change.

@article{Phukkaphan2017HystereticSC,
  title={Hysteretic spin crossover driven by anion conformational change.},
  author={Natnaree Phukkaphan and Dyanne L. Cruickshank and Keith S. Murray and Wasinee Phonsri and Phimphaka Harding and David J. Harding},
  journal={Chemical communications},
  year={2017},
  volume={53 70},
  pages={
          9801-9804
        }
}
A new air stable FeIII spin crossover (SCO) complex has been synthesized. The compound undergoes abrupt SCO near room temperature with T1/2 (↓) = 244 K and T1/2 (↑) = 278 K. Structural studies of the complex in the high spin and low spin state show that the strong cooperativity and thus the wide hysteresis is driven by an unprecedented anionic conformational change. 
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References

SHOWING 1-10 OF 46 REFERENCES
Cooperative spin transition in a mononuclear manganese(III) complex.
Mind the gap: A complete, cooperative spin transition for a mononuclear Mn(III) complex is reported with an 8 K hysteresis window. Raman spectra collected at a single temperature in warming and…
Abrupt two-step and symmetry breaking spin crossover in an iron(III) complex: an exceptionally wide [LS-HS] plateau.
[Fe(qsal-Br)2]NO3·2MeOH is reported which undergoes abrupt two step symmetry breaking spin crossover, T½(1st step) = 136 K and T½(2nd step) = 232 K with a hysteresis of 16 K and 5 K, respectively,…
Cooperative spin transition in a lipid layer like system.
TLDR
Crystal structure analysis in both low-spin and high-spin states reveals a lipid layer-like arrangement of the complex molecules and provides insights into the spin switching mechanism.
An iron(II) spin-crossover complex with a 70 K wide thermal hysteresis loop.
TLDR
Hydrogen bonds are used as intermolecular contacts in SCO complexes with N4O2 coordination spheres to transmit cooperative interactions through H bonds, as these should be stronger than van der Waals contacts but more flexible than covalent linkers.
Heterometallic Fe(III) /K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature.
TLDR
X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure, contrary to previous reports of broad thermal hysteresis induced by coordination bonds of Fe(II) spin crossover coordination polymers (with 1D/3D structures).
Spin crossover in iron(III) complexes
Spin-crossover Compounds with Wide Thermal Hysteresis
Spin-crossover compounds showing wide thermal hysteresis are surveyed, and the factors underlying these properties are discussed. Hysteresis is promoted by large structural rearrangements during the…
Synergistic spin transition between spin crossover and spin-Peierls-like singlet formation in the halogen-bonded molecular hybrid system: [Fe(Iqsal)2 ][Ni(dmit)2 ]⋅CH3 CN⋅H2 O.
TLDR
To introduce halogen-bond interactions between a cation and an anion, a novel Fe(III) complex from iodine-substituted ligands involving a paramagnetic nickel dithiolene anion was prepared and characterized and showed the light-induced excited spin state trapping effect.
Pressure effect studies on spin crossover and valence tautomeric systems
In the present review chapter we discuss the results of investigations of the influence of hydrostatic pressure (up to 1.2 GPa) on the spin transition behaviour in coordination compounds of 3d…
Thermal spin-crossover with a large hysteresis spanning room temperature in a mononuclear complex.
TLDR
A new compound showing a large spin-crossover hysteresis spanning room temperature demonstrates in a definitive manner that this goal is achievable in molecular discrete compounds without damaging the single-crystal character.
...
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2
3
4
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