Spin transition in [Fe(phen)2(NCS)2] and [Fe(bipy)2(NCS)2]: Hysteresis and effect of crystal quality

Müller, Erwin W.; Spiering, H.; Gütlich, P.

doi:10.1016/0009-2614(82)83731-7

Cited by 130 publications

(46 citation statements)

References 16 publications

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“…The behavior of spin crossover shows an abrupt temperature dependence with a very wide thermal hysteresis ͑about 60 K͒, almost several hundred times larger than ͓Fe͑phen͒ 2 ͑NCS͒ 2 ] does. 7 The existence of hysteresis, as proven in the previous works, 1,8,9 establishes that spin transition proceeds as first-order phase transition and present of cooperative effects. In this work, we showed the realization of HS metastable state at low temperatures by rapid cooling; the study of spin transition by controlling speed of cooling or warming; and the influence from magnetic field in the spin transition.…”

mentioning

confidence: 79%

Rapid cooling and magnetic field-induced cooperative effect for the metastable quintet state in a spin crossover complex

Liu

Jiang

et al. 1999

Applied Physics Letters

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mentioning

confidence: 79%

Rapid cooling and magnetic field-induced cooperative effect for the metastable quintet state in a spin crossover complex

Liu

Jiang

et al. 1999

Applied Physics Letters

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“…This resulted in a pronounced reduction in cooperative behaviour and the eventual suppression of all SCO properties. 13,14 Thus, careful comparison of SCO properties arising from mechanochemical and solution-state synthetic protocols (via SQUID magnetometry) is required to ensure functionality of the produced materials is not deleteriously affected by grinding. The SCO behaviour of solution-synthesized 1 (denoted 1 sol ) as a function of temperature is shown in Fig.…”

Section: (F)mentioning

confidence: 99%

Mechanochemical synthesis of cooperative spin crossover materials

Askew

Shepherd

2018

Chem. Commun.

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We describe the synthesis of switchable spin crossover materials via mechanochemistry for the first time. Three chemically diverse spin crossover materials have been produced using solvent-free grinding.Crucially, cooperative spin transition behavior and crystallinity is retained, presenting exciting opportunities for the discovery of new materials with switchable magnetic, optical and structural properties.Spin crossover (SCO) materials have seen a surge in interest in recent years as a result of their optical, magnetic and structural bistability in technologically accessible temperature ranges, giving rise to a number of potential applications in sensing, display and actuator technologies.1,2 The bistability in these systems stems from their propensity to switch reversibly between high-spin (HS) and low-spin (LS) states in response to physical stimuli including temperature, pressure, light irradiation, guest molecules and magnetic field. 3 There are hundreds of known SCO-active materials in the literature including molecular coordination complexes, 1D coordination polymers and 2-/3-dimensional metal organic frameworks. The cooperativity of the SCO phenomenon (abruptness of the transition, hysteretic effects etc.) is a result of electron-phonon coupling between SCO centers in the solid state through elastic interactions in the lattice. 4 The degree of cooperativity is important for application, and has been shown to be sensitive to the crystallinity of the material, particle size and the presence of solvents in the lattice. 2,5 Synthesis of bulk SCO materials has typically been carried out via traditional solution state chemistry, although more complex techniques for the production of nanoparticles and thin films have been developed in the last decade. Remarkably, all existing techniques use solvents and can be timeconsuming; often requiring inert atmospheres and multiple synthetic steps. This aspect is particularly limiting in the search for new SCO-active materials. Herein, we present for the first time the rapid and facile synthesis of three chemically different classes of SCO material, using mechanochemical techniques. We show that microcrystalline samples of SCO-active molecular materials, 1D coordination networks and 3D MOFs can be produced using this technique and crucially the cooperative behaviour of the spin transition is maintained. Finally, we highlight how this technique can be used to accelerate SCO research. Mechanochemistry refers to the reaction of materials through the application of mechanical energy, often through grinding in the solid state. While mechanochemistry has long been used in the synthesis of inorganic materials and composites, in recent years it has also been applied in the synthesis of molecular systems, coordination complexes and frameworks, co-crystals and supramolecular networks. 7,8 Mechanistic explanations for the success of the mechanochemical approach are numerous and as yet no single model can be applied to the varied range of systems that can be produced in this manner....

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“…A few anomalous examples have already been reported in literature when the hysteresis width was found to increase under pressure [24,[37][38][39][40][41][42]. The most obvious explanation of this phenomenon can be a pressure induced additional structural change, since the sharp discontinuity in the phase diagram below 0.5 kbar, followed by a "regular" ClausiusClapeyron behaviour above 0.5 kbar is very difficult to explain in any other ways.…”

Section: Hs Lsmentioning

confidence: 99%

Temperature and pressure effects on the spin state of ferric ions in the [Fe(sal2-trien)][Ni(dmit)2] spin crossover complex

Szilágyi¹,

Dorbes²,

Molnár³

et al. 2008

Journal of Physics and Chemistry of Solids

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This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. A c c e p t e d m a n u s c r i p t

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Spin transition in [Fe(phen)2(NCS)2] and [Fe(bipy)2(NCS)2]: Hysteresis and effect of crystal quality

Cited by 130 publications

References 16 publications

Rapid cooling and magnetic field-induced cooperative effect for the metastable quintet state in a spin crossover complex

Rapid cooling and magnetic field-induced cooperative effect for the metastable quintet state in a spin crossover complex

Mechanochemical synthesis of cooperative spin crossover materials

Temperature and pressure effects on the spin state of ferric ions in the [Fe(sal2-trien)][Ni(dmit)2] spin crossover complex

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