Defying the inverse energy gap law: a vacuum-evaporable Fe(<scp>ii</scp>) low-spin complex with a long-lived LIESST state

Tuczek, Felix; Grunwald, Jan; Torres, Juan F.; Buchholz, Axel; Näther, Christian; Spieker, Lea; Gruber, Manuel; Rohlf, Sebastian; Thakur, Sangeeta; Wende, Heiko; Plass, Winfried; Kuch, W.

doi:10.1039/d3sc00561e

Cited by 2 publications

(1 citation statement)

References 156 publications

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“…Except for ([H 2 B(pz)(pzpy] − ), which is a meridional tridentate ligand, all of them act as facial ones. Still, there are a few other meridional tridentate ones not based on pyrazolylborate, such as ([pypypyr] − ), ([qnal] − ), and ([ t Bu 2 qsal] − ). − In contrast, the use of the bidentate dihydrobispyrazolylborate ([H 2 B(pz) 2 ] − ) ligand introduces a degree of freedom to the system, generating a rich variety of [Fe(H 2 B(pz) 2 ) 2 (L′)] heteroleptic SCO complexes, being L′ chelate bidentate α-diimine ligands derived from either 1,10-phenanthroline or 2,2′-bipy − and other related such as tzpy, btz, and bt (Scheme ). Also, few additional SCO complexes have also been selected to assess their suitability as sublimable materials. − …”

Section: Introductionmentioning

confidence: 99%

Design and Processing as Ultrathin Films of a Sublimable Iron(II) Spin Crossover Material Exhibiting Efficient and Fast Light-Induced Spin Transition

Gavara-Edo,

Valverde-Muñoz,

Muñoz

et al. 2023

Chem. Mater.

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Materials based on spin crossover (SCO) molecules have centered the attention in molecular magnetism for more than 40 years as they provide unique examples of multifunctional and stimuli-responsive materials, which can be then integrated into electronic devices to exploit their molecular bistability. This process often requires the preparation of thermally stable SCO molecules that can sublime and remain intact in contact with surfaces. However, the number of robust sublimable SCO molecules is still very scarce. Here, we report a novel example of this kind. It is based on a neutral iron(II) coordination complex formulated as [Fe(neoim)2], where neoimH is the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline. In the first part, a comprehensive study, which covers the synthesis and magnetostructural characterization of the [Fe(neoim)2] complex as a bulk microcrystalline material, is reported. Then, in the second part, we investigate the suitability of this material to form thin films through high-vacuum sublimation. Finally, the retainment of all present SCO capabilities in the bulk when the material is processed is thoroughly studied by means of X-ray absorption spectroscopy. In particular, a very efficient and fast light-induced spin transition (LIESST effect) has been observed, even for ultrathin films of 15 nm.

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Section: Introductionmentioning

confidence: 99%

Design and Processing as Ultrathin Films of a Sublimable Iron(II) Spin Crossover Material Exhibiting Efficient and Fast Light-Induced Spin Transition

Gavara-Edo,

Valverde-Muñoz,

Muñoz

et al. 2023

Chem. Mater.

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Crystal structure of bis{3-(3,4-dimethoxyphenyl)-5-[6-(pyrazol-1-yl)pyridin-2-yl]-1,2,4-triazol-3-ato}iron(II)–methanol–chloroform (1/2/2)

Znovjyak,

Fritsky,

Sliva

et al. 2023

Acta Cryst E

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The unit cell of the title compound, [Fe(C18H15N6O2)2]·2CH3OH·2CHCl3, consists of a charge-neutral complex molecule, two methanol and two chloroform molecules. In the complex, the two tridentate 2-(5-(3,4-dimethoxyphenyl)-1,2,4-triazol-3-yl)-6-(pyrazol-1-yl)pyridine ligands coordinate to the central FeII ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octahedral coordination sphere. Neighbouring tapered molecules are linked through weak C—H(pz)...π(ph) interactions into one-dimensional chains, which are joined into two-dimensional layers through weak C—H...N/C/O interactions. Furthermore, the layers stack in a three-dimensional network linked by weak interlayer C—H...π interactions of the methoxy and phenyl groups. The intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H...H 32.0%, H...C/C...H 26.3%, H...N/N...H 13.8%, and H...O/O...H 7.5%. The average Fe—N bond distance is 2.185 Å, indicating the high-spin state of the FeII ion. Energy framework analysis at the HF/3–21 G theory level was performed to quantify the interaction energies in the crystal structure.

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Defying the inverse energy gap law: a vacuum-evaporable Fe(ii) low-spin complex with a long-lived LIESST state

Abstract: The novel vacuum-evaporable complex [Fe(pypypyr)2] (pypypyr = bipyridyl pyrrolide) was synthesised and analysed as bulk material and as a thin film. In both cases, the compound is in its low-spin...

Cited by 2 publications

References 156 publications

Design and Processing as Ultrathin Films of a Sublimable Iron(II) Spin Crossover Material Exhibiting Efficient and Fast Light-Induced Spin Transition

Design and Processing as Ultrathin Films of a Sublimable Iron(II) Spin Crossover Material Exhibiting Efficient and Fast Light-Induced Spin Transition

Crystal structure of bis{3-(3,4-dimethoxyphenyl)-5-[6-(pyrazol-1-yl)pyridin-2-yl]-1,2,4-triazol-3-ato}iron(II)–methanol–chloroform (1/2/2)

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