Photoinduced Magnetization of the Cyano-Bridged 3d−4f Heterobimetallic Assembly Nd(DMF)₄(H₂O)₃(μ-CN)Fe(CN)₅·H₂O (DMF = N,N-Dimethylformamide)

Abstract

Photoinduced magnetization of the cyano-bridged 3d-4f heterobimetallic assembly Nd(DMF)4(H2O)3(mu-CN)Fe(CN)5.H2O (1) (DMF = N,N-dimethylformamide) is described in this paper. The chiMT values are enhanced by about 45% after UV light illumination in the temperature range of 5-50 K. We propose that UV light illumination induces a structural distortion in 1. This small structural change is propagated by molecular interactions in the inorganic network. Furthermore, the cooperativity resulting from the molecular interaction functions to increase the activation energy of the relaxation processes, which makes observation of the photoexcited state possible. The flexible network structure through the hydrogen bonds in 1 plays an essential role for the photoinduced phenomenon. This finding may open up a new domain for developing the molecule-based magnetic materials.

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.…”

“…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].…”

Influence of Water Molecules on Properties of Binuclear or Bridged Structures for Chiral CuII-NiII, CuII-PdII, and CuII-PtIITetracyano-Bimetallic Assemblies

“…In recent years, cyanide-bridged coordination polymers [1,2] and their various functions and multifunctions such as photomagnets [3][4][5][6][7] and chiral magnets [8][9][10][11][12][13][14], including N,N'-dimethyl-cyclohexane-1,2-diamine ligands [14], have been studied vigorously. From the viewpoint of crystal engineering, structural dimensionality, flexibility (static structural strain and dynamic structural changes by external physical stimulus), and tuning of electronic properties by these factors are important things for rational design of functional materials.…”

Thermally-Accessible Lattice Strain and Local Pseudo Jahn-Teller Distortion in Various Dimensional CuII-MIII Bimetallic Cyanide-Bridged Assemblies

“…In particular, multi-functional cyanide-bridged molecule-based magnetic materials [3,4] such as photomagnets [5][6][7][8], chiral magnets [9][10][11][12][13], and magnetic conductors [14] have attracted much attention from potential applications functional devices. Molecular design including electronic functions of cyanide-bridged metal complexes is still challenging task in the field of crystal engineering of organic-inorganic frameworks or coordination polymers.…”