Tuning the spin crossover above room temperature: iron(II) complexes of substituted and deprotonated 2,6-bis(benzimidazol-2-yl)pyridine

Boča, Roman; Renz, Franz; Boča, Miroslav; Fueß, H.; Haase, Wolfgang; Kickelbick, Guido; Linert, Wolfgang; Vrbová-Schikora, Martina

doi:10.1016/j.inoche.2004.12.014

Cited by 49 publications

(18 citation statements)

References 12 publications

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“…Unfortunately, complexes of the first family are very difficult to structurally characterize , . Different complexes with spin transitions above 400 K have been reported, but they are often weakly cooperative and gradual in nature.…”

Section: Introductionmentioning

confidence: 99%

Cooperative High‐Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion

Gural'skiy¹,

Golub²,

Shylin³

et al. 2016

Eur J Inorg Chem

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Spin transitions are a spectacular example of molecular switching that can provoke extreme electronic and structural reorganizations in coordination compounds. A new 3D cyanoheterometallic framework, [Fe(pz){Au(CN) 2 } 2 ], has been synthesized in which a highly cooperative spin crossover has been observed at 367 and 349 K in heating and cooling modes, respectively. Mössbauer spectroscopy revealed a complete transi- [a]

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Section: Introductionmentioning

confidence: 99%

Cooperative High‐Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion

Gural'skiy¹,

Golub²,

Shylin³

et al. 2016

Eur J Inorg Chem

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“…The latter has the advantage that in many occasions, SPTs take place with persistence of crystal integrity, which allows their detailed study by single crystal X-ray diffraction (SCXRD). 14,[20][21] The novel heteroleptic Fe(II) complex [FeL(bbp)](ClO4)2 (1, L=2,6-bis-(5-(2-methoxophenyl)-pyrazol-3-yl)-pyridine, 20 bbp= 2,6-bis-(benzimidazol-2-yl)-pyrazol-3-yl)-pyridine); [22][23] Scheme 1), exhibits a remarkable succession of SCO profiles most of them connected to SPTs. The fact that the transformations occur in a single-crystalto-single-crystal (SCSC) manner allows their monitoring by means of SCXRD.…”

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confidence: 99%

A Spin-Crossover Molecular Material Describing Four Distinct Thermal Pathways

et al. 2018

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Spin-crossover (SCO) molecular solids are valued switchable materials for their common abrupt and reversible thermal transitions, large thermal hysteresis, or guest-dependent effects. These properties usually involve crystallographic transitions coupled to the SCO events. These phenomena are of great value for the understanding of solid-state transformations and also for exploiting them. We present here a lattice of the complex [FeL(bbp)](ClO) (1; L and bbp are tris-imine ligands) featuring an unprecedented rich succession of SCO and crystallographic phase transformations. Magnetometry measurements unveil a thermally irreversible sequence of spin conversions that delineate four different thermal pathways. All of these are single-crystal-to-single-crystal processes and can thus be monitored by single crystal X-ray diffraction using one unique specimen. Fresh crystals of 1 contain one molecule of acetone per Fe center (1·ac) that abandons the lattice upon warming at the same time that a SCO from an ordered mixed spin state (1:1 high spin/low spin; HS/LS) to a fully HS state, 1, occurs. This crystallographic phase, accessed through a template effect by the solvent, converts into another one, 1, upon cooling, as triggered by a HS to LS SCO. Warming of 1 induces a new SCO (LS to ordered HS/LS) coupled to another crystallographic phase transition, 1 → 1. The fully HS state of 1 can not be reached before decomposition of the compound. Instead, this phase cycles between the HS/LS and the LS states through superimposable pathways, different from that of the prerequired 1 → 1 phase change. Analysis of the thermal variation of the free energy, G, through density functional theory methods provides trends in agreement with the observation of these transformations and clarifies the possible metastable nature of the various phases identified. This unique behavior allows the access to four different magnetic responses depending on the thermal history of the sample, within a given range of temperatures near the ambient conditions.

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“…Hence, uniquely, the unit cell volume of 10 is almost identical in both spin states. 49,50 The only other molecular compounds known to exhibit symmetric spin transitions with ¦T > 30 K are 11 26 …”

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confidence: 99%

Spin-crossover Compounds with Wide Thermal Hysteresis

2014

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Spin-crossover compounds showing wide thermal hysteresis are surveyed, and the factors underlying these properties are discussed. Hysteresis is promoted by large structural rearrangements during the transition and by strong intermolecular interactions involving rigid ligand groups or donor atoms. These observations provide new principles for the design of molecular crystals undergoing spin crossover (or other phase changes) with predefined switching properties.

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Tuning the spin crossover above room temperature: iron(II) complexes of substituted and deprotonated 2,6-bis(benzimidazol-2-yl)pyridine

Cited by 49 publications

References 12 publications

Cooperative High‐Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion

Cooperative High‐Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion

A Spin-Crossover Molecular Material Describing Four Distinct Thermal Pathways

Spin-crossover Compounds with Wide Thermal Hysteresis

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