Hysteretic spin crossover in isomeric iron(<scp>ii</scp>) complexes

Bushuev, Mark B.; Krivopalov, V. P.; Николаенкова, Елена Б.; Vinogradova, Katerina A.; Gatilov, Yuri V.

doi:10.1039/c8dt02223b

Cited by 10 publications

(13 citation statements)

References 53 publications

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“…The main geometrical features of zinc(II) coordination polymer of formula [Zn2Cl4(C6H9N3O2)2]n are reported in Tables 2 and 3 tetrahedron (Table 2). These values are similar to those reported for other tetrahedral Zn(II) complexes such as 2-[(2-aminoethyl)amino]ethanaminium dichlorozincate [30] and 4-(3,5diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine dichlorozincate complexes [31]. The geometry of four-coordinated metal complex my conveniently be measured by the Yang 4parameter [32], 4 = [360 -(β + α)]/141 with β and α being the two largest angles, that is zero for a perfect square planar geometry and one for a perfect tetrahedral geometry.…”

Section: Structure Descriptionsupporting

confidence: 88%

A new 1D Zn(II) coordination polymer containing 2-amino-4,6-dimethoxypyrimidine ligand: crystal structure, Hirshfeld surface analysis, and physicochemical studies

Boubakri

Jelsch²,

Lucas

et al. 2020

Journal of Molecular Structure

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Section: Structure Descriptionsupporting

confidence: 88%

A new 1D Zn(II) coordination polymer containing 2-amino-4,6-dimethoxypyrimidine ligand: crystal structure, Hirshfeld surface analysis, and physicochemical studies

Boubakri

Jelsch²,

Lucas

et al. 2020

Journal of Molecular Structure

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“…Although it is possible to perform magnetometry studies in the presence of solvent vapor to avoid lattice solvent desorption‐mediated SCO alteration, [14] such studies are out of the scope of the present investigation. As the main focus of this study is the elucidation of structure‐SCO property relation.…”

Section: Resultsmentioning

confidence: 99%

Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes

Kumar

Suryadevara

Mizuno

et al. 2022

Chemistry A European J

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Bistable spin-crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT 1/2 ) spin-state switching are desirable for molecule-based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)-2,6-bis62 K -is observed for 1, whereas 2 undergoes above-room-temperature lattice-solvent content-dependent SCO -T 1/2 = 331 K; ΔT 1/2 = 43 K. Variable-temperature single-crystal X-ray diffraction studies of the complexes revealed pronounced molecular reorganizations -from the Jahn-Teller-distorted HS state to the less distorted LS state -and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule-based switching and memory elements.

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“…Further modification of the ligand by a change from pyridine to pyrazine as the central ring does not show a significant difference in the SCO properties . More recent examples report bidentate isomeric ligands used to obtain iron(II) showing SCO; however, the same combined effects (LF/packing) cannot be easily isolated. , …”

Section: Introductionmentioning

confidence: 97%

“…46 More recent examples report bidentate isomeric ligands used to obtain iron (II) showing SCO; however, the same combined effects (LF/packing) cannot be easily isolated. 47,48 The aim of the present work is to achieve better control of the SCO phenomenon by tuning the LF on the metal center through structural isomerism of the ligands without serious perturbation of the packing in the solid state. We will show that small changes in the ligand structure involving the position of a single heteroatom can fully switch the SCO behavior of the complex.…”

Section: ■ Introductionmentioning

confidence: 99%

Switching the Spin-Crossover Phenomenon by Ligand Design on Imidazole–Diazineiron(II) Complexes

et al. 2018

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The iron(II) complexes of two structural isomers of 2-(1H-imidazol-2-yl)diazine reveal how ligand design can be a successful strategy to control the electronic and magnetic properties of complexes by fine-tuning their ligand field. The two isomers only differ in the position of a single diazinic nitrogen atom, having either a pyrazine (Z) or a pyrimidine (M) moiety. However, [Fe(M)3](ClO4)2 is a spin-crossover complex with a spin transition at 241 K, whereas [Fe(Z)3](ClO4)2 has a stable magnetic behavior between 2 and 300 K. This is corroborated by temperature-dependent Mössbauer spectra showing the presence of a quintet and a singlet state in equilibrium. The temperature-dependent single-crystal X-ray diffraction results relate the spin-crossover observed in [Fe(M)3](ClO4)2 to changes in the bond distances and angles of the coordination sphere of iron(II), hinting at a stronger σ donation of ligand Z in comparison to ligand M. The UV/vis spectra of both complexes are solved by means of the multiconfigurational wave-function-based method CASPT2 and confirm their different spin multiplicities at room temperature, as observed in the Mössbauer spectra. Calculations show larger stabilization of the singlet state in [Fe(Z)3]2+ than in [Fe(M)3]2+, stemming from the slightly stronger ligand field of the former (506 cm–1 in the singlet). This relatively weak effect is indeed capable of changing the spin multiplicity of the complexes and causes the appearance of the spin transition in the M complex.

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Hysteretic spin crossover in isomeric iron(ii) complexes

Abstract: Two mononuclear iron(ii) complexes with isomeric N,N,N-tridentate pyrimidine-based ligands were synthesized. Both complexes show reproducible hysteretic spin crossover. Low spin state to high spin state switching is cooperative due to autocatalysis.

Cited by 10 publications

References 53 publications

A new 1D Zn(II) coordination polymer containing 2-amino-4,6-dimethoxypyrimidine ligand: crystal structure, Hirshfeld surface analysis, and physicochemical studies

A new 1D Zn(II) coordination polymer containing 2-amino-4,6-dimethoxypyrimidine ligand: crystal structure, Hirshfeld surface analysis, and physicochemical studies

Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes

Switching the Spin-Crossover Phenomenon by Ligand Design on Imidazole–Diazineiron(II) Complexes

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