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Nanoscale Self-Hosting of Molecular Spin-States in the Intermediate Phase of a Spin-Crossover Material
Ist Teil von
Chemistry : a European journal, 2010-12, Vol.16 (47), p.14060-14068
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2010
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
A new spin‐crossover (SC) complex [FeIIH2L2‐Me][AsF6]2 has been synthesized, in which H2L2‐Me denotes the chirogenic hexadentate N6 Schiff‐base ligand bis{[(2‐methylimidazol‐4‐yl)methylidene]‐3‐aminopropyl}ethylenediamine. This complex has revealed a rich variety of phases during its two‐step thermal crossover, as well as photoinduced spin‐state switching. A high‐symmetry high‐spin (HS, S=2) phase, a low‐symmetry low‐spin (LS, S=0) phase, an intermediate phase characterized by an unprecedented lozenge pattern of 12 predominantly HS molecular crystallographic sites confining 18 predominantly LS molecular crystallographic sites, and a photoinduced low‐symmetry HS phase have been accurately evidenced by temperature‐dependent magnetic susceptibility, Mössbauer spectroscopy, and crystallographic studies. This variety of phases illustrates the multi‐stability of this system, which results from coupling between the electronic states and structural instabilities.
Nanoscale self‐hosting of spin‐state: Thermally induced spin crossover associated with symmetry breaking yields an unprecedented long‐range ordering in the intermediate (INT) phase (supercell structure of 30 molecules) of a novel molecular material based on an iron complex. A remarkable lozenge pattern is produced, including 12 predominantly high‐spin (HS), 8 predominantly low‐spin (LS), and 10 purely LS molecular crystallographic sites (red, purple, and blue, respectively, in figure).