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Symmetry Breaking and Two-Step Spin-Crossover Behavior in Two Cyano-Bridged Mixed-Valence {Fe III 2 (μ-CN) 4 Fe II 2 } Clusters.
- Source :
-
Inorganic chemistry [Inorg Chem] 2019 Nov 04; Vol. 58 (21), pp. 14316-14324. Date of Electronic Publication: 2019 Oct 17. - Publication Year :
- 2019
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Abstract
- Two new cyano-bridged mixed-valence {Fe <superscript>III</superscript> <subscript>2</subscript> (μ-CN) <subscript>4</subscript> Fe <superscript>II</superscript> <subscript>2</subscript> } clusters, {[(Tp)Fe <superscript>III</superscript> (CN) <subscript>3</subscript> ] <subscript>2</subscript> [Fe <superscript>II</superscript> (Py <subscript>2</subscript> N <subscript>2</subscript> )] <subscript>2</subscript> }·(ClO <subscript>4</subscript> ) <subscript>2</subscript> ·MeCN·Et <subscript>2</subscript> O ( 1 ·MeCN·Et <subscript>2</subscript> O), its solvent-free form ( 1 ), and {[(Tp)Fe <superscript>III</superscript> (CN) <subscript>3</subscript> ] <subscript>2</subscript> [Fe <superscript>II</superscript> (Me <subscript>2</subscript> Py <subscript>2</subscript> N <subscript>2</subscript> )] <subscript>2</subscript> }·(ClO <subscript>4</subscript> ) <subscript>2</subscript> ·5MeOH ( 2 ·5MeOH), were obtained [Tp = hydrotris(pyrazol-1-yl)borate; N , N '-bis(2-pyridylmethyl)- N , N '-bis(4-X-benzyl)-1,2-ethanediamine, Py <subscript>2</subscript> N <subscript>2</subscript> , X = H; Me <subscript>2</subscript> Py <subscript>2</subscript> N <subscript>2</subscript> , X = Me]. Complexes 1 and 2 ·5MeOH exhibit gradual thermally induced two-step spin-crossover behavior (SCO) at two Fe <superscript>II</superscript> metal centers, and the transformation of high-spin (HS) to low-spin (LS) Fe <superscript>II</superscript> ions with temperature was confirmed by a combination of X-ray crystallography, variable-temperature Fourier transform infrared, variable-temperature magnetic susceptibility, and <superscript>57</superscript> Fe Mössbauer spectroscopy. Moreover, complexes 1 ·MeCN·Et <subscript>2</subscript> O and 1 exhibit a reversible single-crystal-to-single-crystal transformation, and complex 1 undergoes two-step SCO behavior with T <subscript>1/2</subscript> = 178 and 93 K accompanied by symmetry breaking in the structure.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 58
- Issue :
- 21
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 31622084
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.9b00544