Photomagnetic Switching of the Complex [Nd(dmf)₄(H₂O)₃(μ‐CN)Fe(CN)₅]⋅H₂O Analyzed by Single‐Crystal X‐Ray Diffraction

Abstract

X-ray vision: Single-crystal XRD experiments (see picture) reveal the excited-state structure of the photomagnetic heterobimetallic title complex. The system shows a decrease in all the iron-ligand bond lengths, suggesting that photoexcitation involves a ligand-to-metal charge transfer or a change in the superexchange coupling between the metal centers.

Isotope Effect and Lanthanide Contraction for 3d-4f Cyanide-Bridged Complexes Exhibiting Negative Thermal Expansion

“…Since crystal structure was not determined for them, we investigated TG-DTA for intermolecular hydrogen bonds in crystal lattice and 57 Fe Mössbauer spectra and Fe2p 3/2 and Fe2p 1/2 XAS for coordination environment or electronic states of Fe(III) ions. The experimental results suggested that intermolecular hydrogen bonds was important for this isotope effects found in Nd(DMF) 4 (H 2 O) 3 Fe(CN) 6 •H 2 O.…”

“…Previously, we found that isotope effects of temperature dependence of magnetization for Nd(DMF) 4 (H 2 O) 3 Fe(CN) 6 •H 2 O with 2 H-substituted H 2 O and DMF ligands [6]. Since crystal structure was not determined for them, we investigated TG-DTA for intermolecular hydrogen bonds in crystal lattice and 57 Fe Mössbauer spectra and Fe2p 3/2 and Fe2p 1/2 XAS for coordination environment or electronic states of Fe(III) ions.…”

“…Recently, various 3d-4f molecule-based magnets such as Ln(DMF) 4 (H 2 O) 3 M(CN) 6 •H 2 O have been investigated widely [1,2]. The first photo-controllable 3d-4f moleculebased magnets was Nd(DMF) 4 (H 2 O) 3 Fe(CN) 6 •H 2 O [3], and its crystal structure of photo-excited state was also determined [4].…”

“…The first photo-controllable 3d-4f moleculebased magnets was Nd(DMF) 4 (H 2 O) 3 Fe(CN) 6 •H 2 O [3], and its crystal structure of photo-excited state was also determined [4]. Besides magnetic properties, we have systematically studied on Ln(DMF) 4 (H 2 O) 3 M(CN) 6 •H 2 O and related compounds in view of structure-function correlation due to lanthanide contraction and application for hybrid functional materials [5].…”

Multiple Magnetization Reversal Channels Observed in a 3d-4f Single Molecule Magnet

“…A detailed view of the coordination sphere of the Dy III center is reported as reference in Figure 1: Dy III coordination number is eight, and analysis of the coordination polyhedron via use of SHAPE [18] provided evidence of a geometry intermediate between square antiprismatic, bicapped trigonal prismatic and trigonal dodecahedron geometry (see Table S1). The analysis of the packing, as well as detailed X-ray investigation on isostructural systems, [19] showed the existence of a 3D network made up of Dy III -Co III dinuclear entities where the five terminal CN groups of the {Co(CN) 6 } fragment are connected through hydrogen bonds to the Lncoordinated water molecules via crystallization water molecules. The static magnetic properties revealed that this network of hydrogen bonding interaction might result in non-negligible interdimer coupling interactions [17].…”