Room-temperature spin-transition iron compounds

Šalitroš, Ivan; Madhu, N. T.; Boča, Roman; Pavlík, Jan; Rüben, Mario

doi:10.1007/s00706-009-0128-4

Cited by 155 publications

(76 citation statements)

References 103 publications

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“…The average Fe−N bond lengths of 1 Pd are 1.978 and 2.185 Å at 110 and 220 K (Table ), respectively, which are consistent with the LS and HS states of the Fe II ion. The variation of average Fe−N bond lengths between 110 and 220 K is 0.207 Å, substantially manifesting the occurrence of complete SCO . Additionally, the octahedral distortion parameter ( Σ ), defined as the sum of |90°− θ | for the twelve cis ‐N‐Fe‐N angles in the coordination octahedron, has increased from 6.56° (110 K) to 12.32° (220 K), which is in agreement with SCO behavior from the LS state to HS state (Table S2 in the Supporting Information).…”

Section: Resultssupporting

confidence: 69%

Hysteretic Two‐Step Spin‐Crossover Behavior in Two Two‐Dimensional Hofmann‐Type Coordination Polymers

Liu

Tao

2017

Chemistry A European J

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The reaction of ferrous salts and square-planar tetracyanometallates [M (CN) ] (M=Pd, Pt) with ligand 4-(1H-pyrazol-3-yl)pyridine (Hppy) resulted in the formation of two two-dimensional (2D) Hofmann-like coordination polymers (CPs) with the general formula of {Fe (Hppy) [M (CN) ]}⋅H O (M=Pd for 1 , Pt for 1 ). The two CPs have been studied by variable-temperature single-crystal X-ray crystallography, differential scanning calorimetry, and magnetic measurements. Polymers 1 and 1 are isostructures, in which the Fe atoms are equatorially coordinated with [M (CN) ] to form 2D undulating layers and axially coordinated with Hppy ligands. Both compounds undergo cooperative, complete spin crossover (SCO), with characteristic abrupt and remarkable two equal steps, featuring hysteresis widths of 14 K and 19 K (1 ) and 17 and 23 K (1 ) for the two steps. The SCO cooperativity may result from the hydrogen bonds and π⋅⋅⋅π interactions within and between such 2D layers, and the two-step SCO behavior is accompanied with phase transitions.

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Section: Resultssupporting

confidence: 69%

Hysteretic Two‐Step Spin‐Crossover Behavior in Two Two‐Dimensional Hofmann‐Type Coordination Polymers

Liu

Tao

2017

Chemistry A European J

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“…The near-edge structure of PAC and the changes in the C-D region are rather similar to those reported by Gawelda et al [15] and Sato et al [18,19] for aqueous SCO [Fe(bpy) 3 ] 2 + (bpy = bipyridine) and [Fe(phen) 3 ] 2 + respectively, in their study of light-induced spin transition. Like our materials, these systems belong to the class of nitrogen 6-coordinated mononuclear iron(II) complexes and possess a LS ground configuration.…”

Section: Introductionsupporting

confidence: 75%

X‐Ray Near‐Edge Absorption Study of Temperature‐Induced Low‐Spin‐to‐High‐Spin Change in Metallo‐Supramolecular Assemblies

et al. 2010

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X-ray absorption near the iron K edge (XANES) was used to investigate the characteristics of temperature-induced low-spin-to-high-spin change (SC) in metallo-supramolecular polyelectrolyte amphiphile complexes (PAC) containing FeN(6) octahedra attached to two or six amphiphilic molecules. Compared to the typical spin-crossover material Fe(phen)(2) (NCS)(2) XANES spectra of PAC show fingerprint features restricted to the near-edge region which mainly measures multiple scattering (MS) events. The changes of the XANES profiles during SC are thus attributed to the structure changes due to different MS path lengths. Our results can be interpreted by a uniaxial deformation of FeN(6) octahedra in PAC. This is in agreement with the prediction that SC is originated by a structural phase transition in the amphiphilic matrix of PAC, but in contrast to Fe(phen)(2) (NCS)(2), showing the typical spin crossover being associated with shortening of all the metal-ligand distances.

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“…In a properly designed system, a thermally driven SCO can be centered around room temperature. A limited number of such metal complexes were nicely reviewed by Ruben et al . Thus, the thermally induced switching of physical properties of those materials becomes feasible at nearly room temperature.…”

Section: Introductionmentioning

confidence: 99%

How to Switch Spin‐Crossover Metal Complexes at Constant Room Temperature

Khusniyarov

2016

Chemistry A European J

120

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Spin-crossover metal complexes represent a highly promising class of molecular switches, the diverse physicochemical properties of which can be reversibly changed by different physical and chemical stimuli. One of the most interesting and examined features of these materials is the change of magnetic properties by changing the temperature or by irradiation with light at low temperatures. However, most prospective applications of such complexes require functioning at room temperature. This Concept article provides an overview about how the switching of spin-crossover metal complexes can be achieved at constant room temperature. The principles of switching by different physical and chemical methods in solution and in the solid state are presented in an easy-to-read form for nonspecialists. These are further supported and clarified by examples from the literature. The overview might also be interesting for experts that target spin-crossover systems functioning at ambient conditions.

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Room-temperature spin-transition iron compounds

Cited by 155 publications

References 103 publications

Hysteretic Two‐Step Spin‐Crossover Behavior in Two Two‐Dimensional Hofmann‐Type Coordination Polymers

Hysteretic Two‐Step Spin‐Crossover Behavior in Two Two‐Dimensional Hofmann‐Type Coordination Polymers

X‐Ray Near‐Edge Absorption Study of Temperature‐Induced Low‐Spin‐to‐High‐Spin Change in Metallo‐Supramolecular Assemblies

How to Switch Spin‐Crossover Metal Complexes at Constant Room Temperature

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