Switching Magnetic Properties by a Mechanical Motion

Doistau, Benjamin; Benda, Lorien; Hasenknopf, Bernold; Marvaud, Valérie; Vives, Guillaume

doi:10.3390/magnetochemistry4010005

Cited by 16 publications

(13 citation statements)

References 78 publications

(94 reference statements)

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“…Actually, fragmentation appears to be the rule rather than the exception on metals, and consequently further investigations in that direction have already started. Different strategies are explored in parallel, consisting in the synthesis of more robust compounds [25] and the development of new spin switching designs involving mechanical motion [102][103][104] or hydrogen abstraction [105,106]. In addition, SCO complexes incorporating a functional switchable ligand have been reported [44] and hold great promises.…”

Section: Discussionmentioning

confidence: 99%

Spin-Crossover Complexes in Direct Contact with Surfaces

Gruber

Berndt

2020

Magnetochemistry

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The transfer of the inherent bistability of spin crossover compounds to surfaces has attracted considerable interest in recent years. The deposition of the complexes on surfaces allows investigating them individually and to further understand the microscopic mechanisms at play. Moreover, it offers the prospect of engineering switchable functional surfaces. We review recent progress in the field with a particular focus on the challenges and limits associated with the dominant experimental techniques used, namely near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). One of the main difficulties in NEXAFS-based experiments is to ascertain that the complexes are in direct contact with the surfaces. We show that molecular coverage determination based on the amplitude of the edge-jump of interest is challenging because the latter quantity depends on the substrate. Furthermore, NEXAFS averages the signals of a large number of molecules, which may be in different states. In particular, we highlight that the signal of fragmented molecules is difficult to distinguish from that of intact and functional ones. In contrast, STM allows investigating individual complexes, but the identification of the spin states is at best done indirectly. As quite some of the limits of the techniques are becoming apparent as the field is gaining maturity, their detailed descriptions will be useful for future investigations and for taking a fresh look at earlier reports.

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Section: Discussionmentioning

confidence: 99%

Spin-Crossover Complexes in Direct Contact with Surfaces

Gruber

Berndt

2020

Magnetochemistry

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“…Molecules exhibiting switchable magnetic properties have been extensively studied over the last few decades in the context of the miniaturization of electronics, sensors, and memory devices. − This particular field of magnetic switching has been the subject of major developments fueled by numerous research activities focused on molecular spin crossover (SCO) materials − and single-molecule magnets. − Most examples described so far are crystalline solids obtained from first-row transition-metal complexes ( d 4 to d 7 ) capable of undergoing spin-state transition as a response to external physical perturbations such as temperature, pressure, and light. ,, From a practical point of view, SCO phenomena are quite often difficult to explain from well-defined molecular events and they are also strongly dependent on cooperativity processes that happen to be enhanced in the solid state and at low temperatures. , SCO systems are therefore usually studied in solid crystals, although recent reports have shown that similar processes can occur in solution and at near-ambient temperatures. ,− …”

Section: Introductionmentioning

confidence: 99%

Ni-Centered Coordination-Induced Spin-State Switching Triggered by Electrical Stimulation

et al. 2022

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We herein report the synthesis and magnetic properties of a Ni(II)-porphyrin tethered to an imidazole ligand through a flexible electron-responsive mechanical hinge. The latter is capable of undergoing a large amplitude and fully reversible folding motion under the effect of electrical stimulation. This redox-triggered movement is exploited to force the axial coordination of the appended imidazole ligand onto the square-planar Ni(II) center, resulting in a change in its spin state from low spin (S = 0) to high spin (S = 1) proceeding with an 80% switching efficiency. The driving force of this reversible folding motion is the π-dimerization between two electrogenerated viologen cation radicals. The folding motion and the associated spin state switching are demonstrated on the grounds of NMR, (spectro)electrochemical, and magnetic data supported by quantum calculations.

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“…Among all types of spin transition (ST), the first-order spin crossover, which has a large hysteresis width and a transition temperature T 1/2 at room temperature, has the most potential for application. Since most ST cannot directly meet the actual application, it is an urgent task to study the possibility of precise regulation of ST. − The use of both various external physical stimuli, such as temperature, pressure, − ,− light, − magnetic field, , and X-ray radiation, and chemical, such as the structural modification and replacement of coordinated metal ligands, organic radicals, or metals, − can change the properties of the complex in a wide range and then regulate the ST phenomenon.…”

Section: Introductionmentioning

confidence: 99%

Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds

Li¹,

Каліта²,

Fylymonov³

et al. 2022

Inorg. Chem.

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Recently, the possibility of exploiting the phenomenon of spin transition (ST) has been intensively investigated; therefore, it is particularly important to study the behavior of ST under various stimuli. Here, the shape and content of the intermediate phase of ST in Hoffmann-like compounds [Fe(Fpz) 2 M(CN) 4 ] (M = Pt, Pd) under external stimuli are studied. For this purpose, magnetic and Raman spectroscopy studies were carried out. In pressure-induced spin transition (PIST), a mixture of high-spin and low-spin states appears, while in temperature-induced spin transition (TIST), a homogeneous state occurs. The first-order ST induced by pressure has a hysteresis but is not abrupt. However, the temperature-induced spin transition at ambient pressure is hysteretic and abrupt. To investigate this difference, we discuss using a thermodynamic model that considers elastic interactions, showing that the slope of the hysteresis loop is related to the appearance of internal pressure, which is related to the difference in sample compressibility under high-spin and low-spin states.

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Switching Magnetic Properties by a Mechanical Motion

Cited by 16 publications

References 78 publications

Spin-Crossover Complexes in Direct Contact with Surfaces

Spin-Crossover Complexes in Direct Contact with Surfaces

Ni-Centered Coordination-Induced Spin-State Switching Triggered by Electrical Stimulation

Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds

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