scholarly journals Spin state switching in iron coordination compounds

2013 ◽  
Vol 9 ◽  
pp. 342-391 ◽  
Author(s):  
Philipp Gütlich ◽  
Ana B Gaspar ◽  
Yann Garcia

The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices. The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property.

2016 ◽  
Vol 45 (36) ◽  
pp. 14008-14018 ◽  
Author(s):  
Daniel Unruh ◽  
Patrick Homenya ◽  
Manish Kumar ◽  
Ralf Sindelar ◽  
Yann Garcia ◽  
...  

Different kinds of stimuli to induce spin crossover in iron compounds are covered, focusing on electromagnetic irradiation-induced spin state switching phenomena in mono- as well as multinuclear coordination compounds.


2014 ◽  
Vol 67 (11) ◽  
pp. 1595 ◽  
Author(s):  
Kelsey A. Schulte ◽  
Stephanie R. Fiedler ◽  
Matthew P. Shores

We report the syntheses, structures, and magnetic properties of cis-[Fe(pizR)2(NCS)2] complexes based on the pyridyl imidazoline ligands 2-(2′-pyridinyl)-4,5-dihydroimidazole (pizH, 1) and 2-(2′-pyridinyl)-4,5-dihydro-1-methylimidazole (pizMe, 2). The ligands, complexes, and magnetic measurements are chosen to separate hydrogen-bonding and intrinsic ligand field properties, so as to improve our understanding of the effect of hydrogen-bonding interactions on spin-state switching. In the solid state, both complexes are high spin between 5 and 300 K. In deuterated methanol and acetonitrile solutions, both complexes show gradual thermal spin crossover. Complex 1, capable of hydrogen bonding, shows solvent-sensitive spin crossover, whereas spin crossover in the methylated analogue 2 is insensitive to solvent identity.


2016 ◽  
Vol 45 (30) ◽  
pp. 12103-12113 ◽  
Author(s):  
V. I. Minkin ◽  
A. A. Starikova ◽  
A. G. Starikov

Heterometallic complexes of 1,10-phenanthroline-5,6-dione exhibiting unprecedented dynamic behaviour due to synchronized thermally induced intramolecular rearrangements were computationally studied.


2014 ◽  
Vol 5 (1) ◽  
Author(s):  
Takuto Matsumoto ◽  
Graham N. Newton ◽  
Takuya Shiga ◽  
Shinya Hayami ◽  
Yuta Matsui ◽  
...  

2016 ◽  
Vol 18 (40) ◽  
pp. 28307-28315 ◽  
Author(s):  
S. Lakhloufi ◽  
M. H. Lemée-Cailleau ◽  
G. Chastanet ◽  
P. Rosa ◽  
N. Daro ◽  
...  

The thermally induced Spin-CrossOver (SCO) undergone by the mononuclear iron(ii) complex [Fe(PM-AzA)2(NCS)2] (PM = N-2′-pyridylmethylene, AzA = 4-(phenylazo)aniline) is fully pictured by a quasi-continuous structural determination all along the spin-state modification within the sample.


2019 ◽  
Author(s):  
Tim Stauch ◽  
Romit Chakraborty ◽  
Martin Head-Gordon

Spin state switching on external stimuli is a phenomenon with wide applicability ranging from molecular electronics to gas activation in nanoporous frameworks. Here we model spin crossover as a function of hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first-row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a five-fold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe<sup>2+</sup> in [Fe(II)(NH<sub>3</sub>)<sub>5</sub>CO]<sup>2+</sup>.


Author(s):  
Pradip Chakraborty ◽  
Mouhamadou Sy ◽  
Houcem Fourati ◽  
Maria Teresa Delgado Pérez ◽  
Mousumi Dutta ◽  
...  

The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)6](BF4)2 spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)6](BF4)2, which stabilizes...


2015 ◽  
Vol 54 (16) ◽  
pp. 7906-7914 ◽  
Author(s):  
Francisco Javier Valverde-Muñoz ◽  
Ana B. Gaspar ◽  
Sergii I. Shylin ◽  
Vadim Ksenofontov ◽  
José A. Real

2016 ◽  
Vol 644 ◽  
pp. 138-141 ◽  
Author(s):  
Constantin Lefter ◽  
Reasmey Tan ◽  
Julien Dugay ◽  
Simon Tricard ◽  
Gábor Molnár ◽  
...  

2014 ◽  
Vol 793 ◽  
pp. 77-83
Author(s):  
Azusa Muraoka ◽  
Kamel Boukheddaden

We performed of Monte Carlo simulations using Ising-like model on two-dimensional core/shell rectangular lattice L×2L for different sizes in order to study the effect of surface and size on the thermal behavior of spin-crossover nanoparticles. The surface effect is accounted for by constraining all the atoms situated in the boundary in the high-spin state as a result of the weak ligand-field prevailing in the coordination shell. This result is similar to square lattice of spin-crossover nanoparticles, and in agreement with experimental data. Such a non-trivial change is explained as due to the competition between the negative pressures induced the high spin state surface and the bulk properties. We also described the way in which the usual occurrence condition of the first-order transition has to be adapted to the nanoscale.


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