Isomorphism between the electro-elastic modeling of the spin transition and Ising-like model with competing interactions: Elastic generation of self-organized spin states

Among the large family of spin-crossover materials, binuclear systems play an important role due to their specific molecular configurations, allowing the presence of multi-step transitions and elastic frustration. Although this issue benefited from a significant number of spin-based theories, there is almost no elastic description of the spin transition phenomenon in binuclear systems. To overcome this deficiency, in this work we develop the first elastic modeling of thermal properties of binuclear spin-crossover solids. At this end, we investigated a finite spin-crossover open chain constituted of elastically coupled binuclear (A = B) blocks, ⋯A=B−A=B−A=B⋯, in which the considered equivalent A and B sites may occupy two configurations, namely low-spin (LS) and high-spin (HS) states. The sites of the binuclear unit interact via an intramolecular spring and couple to the neighboring binuclear units via other springs. The model also includes the change of length inside and between the binuclear units subsequent to the spin state changes. When injecting an elastic frustration inside the binuclear unit in the LS state, competing interactions between the intra- and the inter-binuclear couplings emerge. The latter shows that according to the intra- and inter-binuclear elastic constants and the strength of the frustration, multi-step transitions are derived, for which a specific self-organization of type (HS = HS)-(LS-LS)-(HS = HS)⋯ is revealed and discussed. Finally, we have also studied the relaxation of the metastable photoinduced HS states at low temperature, in which two relaxation regimes with transient self-organized states were identified when monitoring the elastic frustration rate or the ratio of intra- and intermolecular elastic interactions. These behaviors are reminiscent of the thermal dependence of the order parameters of the system. The present model opens several possibilities of extensions of elastic frustrations acting in polynuclear spin-crossover systems, which may lead to other types of spin-state self-organizations and relaxation dynamics.

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Reduction and spin transition of some macrocyclic Fe(III) complexes

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19842579 ◽

1984 ◽

Vol 49 (11) ◽

pp. 2579-2585

Author(s):

Dana M. Wagnerová ◽

Pavel Stopka ◽

Günter Lassmann ◽

Bernd Ebert

Keyword(s):

Catalytic Activity ◽

Spin Transition ◽

Spin States ◽

Monomeric Form ◽

Esr Spectrum

The ESR and absorption spectroscopies were used to study the reduction of Fe(III) tetrasulphophthalocyanine (FeTSP) and Fe(III) chloro-deuteroporphyrin (FeCDP) by ascorbic acisd and cysteine. Only the monomeric form of Fe(III)TSP gives an ESR spectrum, while the dimer is ESR quiet. The complex is low-spin, and is rapidly reduced by both substrates to Fe(II)TSP. The spin states of the complexes are correlated with their catalytic activity in the oxidation of the substrates by dioxygen.

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Spin transition in iron(II) polymeric complexes and their structure at equilibrium and metastable spin states

Nuclear Instruments and Methods in Physics Research Section A Accelerators Spectrometers Detectors and Associated Equipment ◽

10.1016/s0168-9002(99)00689-0 ◽

2000 ◽

Vol 448 (1-2) ◽

pp. 351-357 ◽

Cited By ~ 6

Author(s):

S.B. Erenburg ◽

N.V. Bausk ◽

L.G. Lavrenova ◽

L.N. Mazalov

Keyword(s):

Spin Transition ◽

Spin States ◽

Polymeric Complexes

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Elastic Origin of the Unsymmetrical Thermal Hysteresis in Spin Crossover Materials: Evidence of Symmetry Breaking

Symmetry ◽

10.3390/sym13050828 ◽

2021 ◽

Vol 13 (5) ◽

pp. 828

Author(s):

Mamadou Ndiaye ◽

Nour El Islam Belmouri ◽

Jorge Linares ◽

Kamel Boukheddaden

Keyword(s):

Symmetry Breaking ◽

High Spin ◽

Spin Crossover ◽

Thermal Hysteresis ◽

Spin Transition ◽

Hysteresis Loops ◽

Point Of View ◽

Self Organization ◽

Spin States ◽

Heating And Cooling

The jungle of experimental behaviors of spin-crossover materials contains a tremendous number of unexpected behaviors, among which, the unsymmetrical hysteresis loops having different shapes on heating and cooling, that we often encounter in literature. Excluding an extra effect of crystallographic phase transitions, we study here these phenomena from the point of view of elastic modeling and we demonstrate that a simple model accounting for the bond lengths misfits between the high-spin and low-spin states is sufficient to describe the situation of unsymmetrical hysteresis showing plateaus at the transition only on cooling or on heating branches. The idea behind this effect relates to the existence of a discriminant elastic frustration in the lattice, which expresses only along the high-spin to low-spin transition or in the opposite side. The obtained two-step transitions showed characteristics of self-organization of the spin states under the form of stripes, which we explain as an emergence process of antagonist directional elastic interactions inside the lattice. The analysis of the spin state transformation inside the plateau on cooling in terms of two sublattices demonstrated that the elastic-driven self-organization of the spin states is accompanied with a symmetry breaking.

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Electro-elastic Modelling of the Two-Step High-Spin to Low-Spin Relaxation with Transient Self-Organized Spin States in 2D Spin Crossover Solids

Journal of the Physical Society of Japan ◽

10.7566/jpsj.89.014004 ◽

2020 ◽

Vol 89 (1) ◽

pp. 014004 ◽

Cited By ~ 3

Author(s):

Mamadou Ndiaye ◽

Kamel Boukheddaden

Keyword(s):

High Spin ◽

Spin Relaxation ◽

Spin Crossover ◽

Spin States ◽

Self Organized

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Five 2,6-Di(pyrazol-1-yl)pyridine-4-carboxylate Esters, and the Spin States of their Iron(II) Complexes

Magnetochemistry ◽

10.3390/magnetochemistry5010009 ◽

2019 ◽

Vol 5 (1) ◽

pp. 9 ◽

Cited By ~ 1

Author(s):

Iurii Galadzhun ◽

Rafal Kulmaczewski ◽

and Malcolm A. Halcrow

Keyword(s):

Room Temperature ◽

Spin Crossover ◽

Thermal Hysteresis ◽

Spin Transition ◽

Benzyl Ester ◽

The Other ◽

Spin States ◽

Phenyl Ester ◽

Coupling Reagent ◽

Complex Salts

Two phenyl ester and three benzyl ester derivatives have been synthesized from 2,6-di(pyrazol-1-yl)pyridine-4-carboxylic acid and the appropriate phenyl or benzyl alcohol using N,N’-dicyclohexylcarbodiimide as the coupling reagent. Complexation of the ligands with Fe[BF4]2·6H2O in acetone yielded the corresponding [FeL2][BF4]2 complex salts. Four of the new ligands and four of the complexes have been crystallographically characterised. Particularly noteworthy are two polymorphs of [Fe(L3)2][BF4]2·2MeNO2 (L3 = 3,4-dimethoxyphenyl 2,6-di{pyrazol-1-yl}pyridine-4-carboxylate), one of which is crystallographically characterised as high-spin while the other exhibits the onset of spin-crossover above room temperature. The other complexes are similarly low-spin at low temperature but exhibit gradual spin-crossover on heating, except for an acetone solvate of [Fe(L5)2][BF4]2 (L5 = benzyl 2,6-di{pyrazol-1-yl}pyridine-4-carboxylate), which exhibits a more abrupt spin-transition at T½ = 273 K with 9 K thermal hysteresis.

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Molecular S = 2 High-Spin, S = 0 Low-Spin and S = 0 ⇄ 2 Spin-Transition/-Crossover Nickel(II)-Bis(nitroxide) Coordination Compounds

Inorganics ◽

10.3390/inorganics9020010 ◽

2021 ◽

Vol 9 (2) ◽

pp. 10

Author(s):

Takayuki Ishida ◽

Saki Ito ◽

Yuta Homma ◽

Yukiya Kyoden

Keyword(s):

High Spin ◽

Density Functional ◽

Coupling Parameter ◽

Spin Transition ◽

Coordination Bond ◽

Antiferromagnetic Coupling ◽

Temperature Phase ◽

Spin States ◽

Coordination Structure ◽

Nickel Ion

Heterospin systems have a great advantage in frontier orbital engineering since they utilize a wide diversity of paramagnetic chromophores and almost infinite combinations and mutual geometries. Strong exchange couplings are expected in 3d–2p heterospin compounds, where the nitroxide (aminoxyl) oxygen atom has a direct coordination bond with a nickel(II) ion. Complex formation of nickel(II) salts and tert-butyl 2-pyridyl nitroxides afforded a discrete 2p–3d–2p triad. Ferromagnetic coupling is favored when the magnetic orbitals, nickel(II) dσ and radical π*, are arranged in a strictly orthogonal fashion, namely, a planar coordination structure is characterized. In contrast, a severe twist around the coordination bond gives an orbital overlap, resulting in antiferromagnetic coupling. Non-chelatable nitroxide ligands are available for highly twisted and practically diamagnetic complexes. Here, the Ni–O–N–Csp2 torsion (dihedral) angle is supposed to be a useful metric to describe the nickel ion dislocated out of the radical π* nodal plane. Spin-transition complexes exhibited a planar coordination structure in a high-temperature phase and a nonplanar structure in a low-temperature phase. The gradual spin transition is described as a spin equilibrium obeying the van’t Hoff law. Density functional theory calculation indicates that the energy level crossing of the high- and low-spin states. The optimized structures of diamagnetic and high-spin states well agreed with the experimental large and small torsions, respectively. The novel mechanism of the present spin transition lies in the ferro-/antiferromagnetic coupling switch. The entropy-driven mechanism is plausible after combining the results of the related copper(II)-nitroxide compounds. Attention must be paid to the coupling parameter J as a variable of temperature in the magnetic analysis of such spin-transition materials. For future work, the exchange coupling may be tuned by chemical modification and external stimulus, because it has been clarified that the parameter is sensitive to the coordination structure and actually varies from 2J/kB = +400 K to −1400 K.

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Compressional behavior and spin state of δ-(Al,Fe)OOH at high pressures

American Mineralogist ◽

10.2138/am-2019-6913 ◽

2019 ◽

Vol 104 (9) ◽

pp. 1273-1284 ◽

Cited By ~ 3

Author(s):

Itaru Ohira ◽

Jennifer M. Jackson ◽

Natalia V. Solomatova ◽

Wolfgang Sturhahn ◽

Gregory J. Finkelstein ◽

...

Keyword(s):

Solid Solution ◽

Spin Crossover ◽

High Pressures ◽

Spin Transition ◽

Heterogeneous Structure ◽

Spin States ◽

Hydrogen Transport ◽

Crossover Region ◽

Volume Collapse ◽

Deep Interior

Abstract Hydrogen transport from the surface to the deep interior and distribution in the mantle are important in the evolution and dynamics of the Earth. An aluminum oxy-hydroxide, δ-AlOOH, might influence hydrogen transport in the deep mantle because of its high stability extending to lower mantle conditions. The compressional behavior and spin states of δ-(Al,Fe3+)OOH phases were investigated with synchrotron X-ray diffraction and Mössbauer spectroscopy under high pressure and room temperature. Pressure-volume (P-V) profiles of the δ-(Al0.908(9)57Fe0.045(1))OOH1.14(3) [Fe/(Al+Fe) = 0.047(10), δ-Fe5] and the δ-(Al0.832(5)57Fe0.117(1))OOH1.15(3) [Fe/(Al+Fe) = 0.123(2), δ-Fe12] show that these hydrous phases undergo two distinct structural transitions involving changes in hydrogen bonding environments and a high- to low-spin crossover in Fe3+. A change of axial compressibility accompanied by a transition from an ordered (P21nm) to disordered hydrogen bond (Pnnm) occurs near 10 GPa for both δ-Fe5 and δ-Fe12 samples. Through this transition, the crystallographic a and b axes become stiffer, whereas the c axis does not show such a change, as observed in pure δ-AlOOH. A volume collapse due to a transition from high- to low-spin states in the Fe3+ ions is complete below 32–40 GPa in δ-Fe5 and δ-Fe12, which i ~10 GPa lower than that reported for pure ε-FeOOH. Evaluation of the Mössbauer spectra of δ-(Al0.824(10)57Fe0.126(4))OOH1.15(4) [Fe/(Al+Fe) = 0.133(3), δ-Fe13] also indicate a spin transition between 32–45 GPa. Phases in the δ-(Al,Fe)OOH solid solution with similar iron concentrations as those studied here could cause an anomalously high ρ/νΦ ratio (bulk sound velocity, defined as K/ρ at depths corresponding to the spin crossover region (~900 to ~1000 km depth), whereas outside the spin crossover region a low ρ/νΦ anomaly would be expected. These results suggest that the δ-(Al,Fe)OOH solid solution may play an important role in understanding the heterogeneous structure of the deep Earth.

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