Cooperativity in spin-crossover transition in metalorganic complexes: Interplay of magnetic and elastic interactions

Banerjee, Hrishit; Kumar, Manoranjan; Saha‐Dasgupta, Tanusri

doi:10.1103/physrevb.90.174433

Cited by 26 publications

(37 citation statements)

References 36 publications

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“…This leads us to conclude that while the magnetic exchanges in the two compounds are of same sign and of similar strengths, the spin-dependent elastic interactions are of ferroelastic nature with significantly larger strength for HAFeF compared to DMAFeF. Following the previous literature 11 we also conclude that primary responsible factor in driving cooperativity in these formate frameworks is the spin-dependent lattice effect, helped by the magnetic exchange. This is different from the case of coordination polymer compounds in which it was found to be entirely driven by the magnetic super-exchanges.…”

Section: Resultssupporting

confidence: 81%

“…To do so, we adopted the same procedure as in Ref. 11 HAFeF. This leads us to conclude that while the magnetic exchanges in the two compounds are of same sign and of similar strengths, the spin-dependent elastic interactions are of ferroelastic nature with significantly larger strength for HAFeF compared to DMAFeF.…”

Section: Resultsmentioning

confidence: 99%

“…This is different from the case of coordination polymer compounds in which it was found to be entirely driven by the magnetic super-exchanges. 11,24 The change of amine cation, leads to the change in cross-linking hydrogen bonding, and thus to the rigidity of the lattices. Interestingly, the change of amine molecule is also found to effect the spin-phonon coupling, thereby producing a profound effect on the cooperativity.…”

Section: Resultsmentioning

confidence: 99%

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Cationic Effect on Pressure Driven Spin-State Transition and Cooperativity in Hybrid Perovskites

2016

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Hybrid or metal organic framework (MOF) perovskites of general composition, ABX 3 , are known to show interesting properties which can lead to variety of technological applications. Our first principles study shows they are also potential candidates for exhibiting cooperative spin-state transitions upon application of external stimuli. We demonstrate this by considering two specific Fe-based MOF perovskites, namely Dimethylammonium Iron Formate, [CH 3 NH 2 CH 3 ][Fe(HCOO) 3 ] and Hydroxylammonium Iron Formate, [NH 3 OH][Fe(HCOO) 3 ]. Both the compounds are found to undergo high-spin (S=2) to low-spin (S=0) transition at Fe(II) site upon application of moderate strength of hydrostatic pressure, along with large hysteresis. This spin-state transition is signaled by the changes in electronic, magnetic and optical properties. We find both the transition pressure and the width of the hysteresis to be strongly dependent of the choice of A-site cation, Dimethylammonium or Hydroxylammonium, implying tuning of spin-switching properties achievable by chemical variation of the amine cation 1 arXiv:1609.01020v1 [cond-mat.mtrl-sci] 5 Sep 2016 in the structure. Our finding opens up novel functionalities in this family of materials of recent interest, which can have important usage in sensors and memory devices.

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Section: Resultssupporting

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Cationic Effect on Pressure Driven Spin-State Transition and Cooperativity in Hybrid Perovskites

2016

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“…This calculation though ignored the spin-phonon coupling, considering the elastic interactions to be spin independent, and thus were unable to distinguish between ferro and antiferroelastic situations. In a recent study, Banerjee et al [71] have studied extensively the microscopic mechanism giving rise to cooperativity in spin crossover considering both the effect of magnetic super-exchange interaction and elastic interactions together with spin-phonon coupling in a coupled 1-d chain model. A model Hamiltonian was setup in the basis of pseudo-spins, corresponding to the elastic part of the interaction, and the actual spin quantum number, describing the magnetic superexchange interaction.…”

Section: Theoretical Models On Cooperativitymentioning

confidence: 99%

Design and Control of Cooperativity in Spin-Crossover in Metal–Organic Complexes: A Theoretical Overview

2017

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Metal organic complexes consisting of transition metal centers linked by organic ligands, may show bistability which enables the system to be observed in two different electronic states depending on external condition. One of the spectacular examples of molecular bistability is the spin-crossover phenomena. Spin-Crossover (SCO) describes the phenomena in which the transition metal ion in the complex under the influence of external stimuli may show a crossover between a low-spin and high-spin state. For applications in memory devices, it is desirable to make the SCO phenomena cooperative, which may happen with associated hysteresis effect. In this respect, compounds with extended solid state structures containing metal ions connected by organic spacer linkers like linear polymers, coordination network solids are preferred candidates over isolated molecules or molecular assemblies. The microscopic understanding, design and control of mechanism driving cooperativity, however, are challenging. In this review we discuss the recent theoretical progress in this direction.

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“…The magnetic cations of organometallic complexes are connected to each other by chemical bridges, and cooperative effects are realized through elastic interaction. In the literature, we have found a few works that discuss cooperative magnetic effects through the exchange interaction between the excited high-spin (HS) states (see., e.g., [21,38]). In all these studies the form of the exchange interaction is postulated phenomenologically, as the Heisenberg exchange interaction with empirical parameters.…”

Section: Introductionmentioning

confidence: 99%

Cooperative phenomena in spin crossover systems

et al. 2017

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Within the framework of a realistic multiband p-d model, we derived an effective Hamiltonian to describe the exchange interaction effects near the spin crossover in magnetic Mott-Hubbard insulators under pressure. It is shown that the single-ion mechanism of spin crossover under the change in the crystal field does not lead to a thermodynamic phase transition; however, at T = 0 a quantum phase transition appears. It has been found that the cooperativity leads to a modification of the quantum phase transition to a first-order phase transition and the appearance of metastable states of the system. The pressure-temperature phase diagram has been obtained to describe the magnetization and high-spin population near the spin crossover of Mott's insulators with d 6 ions.

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Cooperativity in spin-crossover transition in metalorganic complexes: Interplay of magnetic and elastic interactions

Cited by 26 publications

References 36 publications

Cationic Effect on Pressure Driven Spin-State Transition and Cooperativity in Hybrid Perovskites

Cationic Effect on Pressure Driven Spin-State Transition and Cooperativity in Hybrid Perovskites

Design and Control of Cooperativity in Spin-Crossover in Metal–Organic Complexes: A Theoretical Overview

Cooperative phenomena in spin crossover systems

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