Influence of octacyanoniobate(IV)-bridging geometry on Tc in Mn2Nb ferrimagnets of identical 3D topology

Pinkowicz, Dawid; Podgajny, Robert; Nitek, Wojciech; Makarewicz, Magdalena; Czapla, Mariusz; Mihalik, M.; Bałanda, Maria; Sieklucka, Barbara

doi:10.1016/j.ica.2008.03.027

Cited by 27 publications

(12 citation statements)

References 50 publications

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“…For the octacyanometallates, it has been shown that the spin distribution and hence the exchange coupling are significantly influenced by the actual geometry of the {M(CN) 8 } unit. , The Ni−W interaction parameter found here for 1 and 2a are well within the range of what is anticipated for a {W(CN) 8 } unit with square antiprism geometry. , …”

Section: Resultssupporting

confidence: 75%

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(L^Me2Ni−Ln){W(CN)₈}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L^Me2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

et al. 2009

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Assembling bimetallic {Ni-Ln}(3+) units and {W(CN)(8)}(3-) is shown to be an efficient route toward heteronuclear {3d-4f-5d} compounds. The reaction of either the binuclear [{L(Me2)Ni(H(2)O)(2)}{Ln(NO(3))(3)}] complexes or their mononuclear components [L(Me2)Ni] and Ln(NO(3))(3) with (HNBu(3))(3){W(CN)(8)} in dmf followed by diffusion of tetrahydrofuran yielded the trinuclear [{L(Me2)NiLn}{W(CN)(8)}] compounds 1 (Ln = Y), 2a,b (Gd), 3a,b (Tb), 4 (Dy), 5 (Ho), and 6 (Er) as crystalline materials. All of the derivatives possess the trinuclear core resulting from the linkage of the {W(CN)(8)} to the Ni center of the {Ni-Ln} unit. Differences are found in the solvent molecules acting as ligands and/or in the lattice depending on the crystallization conditions. For all the compounds ferromagnetic {Ni-W} and {Ni-Ln} (Ln = Gd, Tb, Dy, and Er} interactions are operative resulting in high spin ground states. Parameterization of the magnetic behaviors for the Y and Gd derivatives confirmed the strong cyano-mediated {Ni-W} interaction (J(NiW) = 27.1 and 28.5 cm(-1)) compared to the {Ni-Gd} interaction (J(NiGd) = 2.17 cm(-1)). The characteristic features for slow relaxation of the magnetization are observed for two Tb derivatives, but these are modulated by the crystal phase. Analysis of the frequency dependence of the alternating current susceptibility data yielded U(eff)/k(B) = 15.3 K and tau(0) = 4.5 x 10(-7) s for one derivative whereas no maxima of chi(M)'' appear above 2 K for the second one.

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Section: Resultssupporting

confidence: 75%

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(L^Me2Ni−Ln){W(CN)₈}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L^Me2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

et al. 2009

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“…Within the layer, [Nb(CN) 8 ] 4– moieties form four cyanide bridges toward the four neighboring Mn complexes. These bridges are located in the B positions of the almost-ideal dodecahedral geometry of [Nb(CN) 8 ] 4– , which ensures a relatively strong intralayer Nb–CN–Mn magnetic coupling attainable in this class of compounds, because of the spin density transferred from the d-metal ion to the π*-orbitals of CN – ligands. − The shortest interlayer metal–metal Mn···Mn distances are 7.5 Å. The above feature led to the long-range magnetic ordering below a relatively high T C = 23.5 K, compared to other 2D and 3D cyanido-bridged Mn II –Nb IV magnets, without a detectable magnetic hysteresis loop.…”

Section: Results and Discussionmentioning

confidence: 99%

Self-Enhancement of Rotating Magnetocaloric Effect in Anisotropic Two-Dimensional (2D) Cyanido-Bridged Mn^II–Nb^IV Molecular Ferrimagnet

et al. 2017

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The rotating magnetocaloric effect (RMCE) is a new issue in the field of magnetic refrigeration. We have explored this subject on the two-dimensional (2D) enantiopure {[Mn(R-mpm)][Nb(CN)]}·4HO (where mpm = α-methyl-2-pyridinemethanol) coordination ferrimagnet. In this study, the magnetic and magnetocaloric properties of single crystals were investigated along the bc//H easy plane and the a*//H hard axis. The observed small easy plane anisotropy is due to the dipole-dipole interactions. For fields higher than 0.5 T, no significant difference in the magnetocaloric effect between both geometries was noticed. The maximal magnetic entropy change for conventional effect was observed at 32 K and the magnetic field change μΔH = 5.0 T attaining the value of ∼5 J mol K. The obtained maximal value of -ΔS is comparable to previously reported results for polycrystalline octacyanidoniobate-based bimetallic coordination polymers. A substantial anisotropy of magnetocaloric effect between the easy plane and hard axis appears in low fields. This includes the presence of inverse magnetocaloric effect only for the a*//H direction. The difference between both geometries was used to study the rotating magnetocaloric effect. We show that the inverse part of magnetocaloric effect can be used to enhance the rotating magnetic entropy change up to 51%. This finding is of key importance for searching efficient materials for RMCE.

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“…10- 16 We have introduced the inorganic-organic hybrid octacyanoniobate(IV)-based networks offering relatively high T c (up to 62 K) together with the opportunity of its tuning on the molecular level. [17][18][19] Parallel to our research, Ohkoshi and co-workers initiated research on the iron(II) SCO (spin-crossover) in Fe II -[Nb IV (CN) 8 (LT phase) between 325-150 K, the latter providing the ferrimagnetically ordered phase below T c = 12 K. Incorporation of the 3-py-CH 2 OH ligand reduces the number of coordination sites at the Fe centre available for cyano-bridging and thus reduces the overall cyano-connectivity, resulting in the T c value lying far beyond the reach of spin-crossover phenomena. molecules, while the second one is dominated by the loss of CNions.…”

Section: Introductionmentioning

confidence: 99%

Iron(II)-octacyanoniobate(IV) ferromagnet with TC 43 K

et al. 2009

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Influence of octacyanoniobate(IV)-bridging geometry on Tc in Mn2Nb ferrimagnets of identical 3D topology

Cited by 27 publications

References 50 publications

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(L^Me2Ni−Ln){W(CN)₈}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L^Me2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(L^Me2Ni−Ln){W(CN)₈}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L^Me2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

Self-Enhancement of Rotating Magnetocaloric Effect in Anisotropic Two-Dimensional (2D) Cyanido-Bridged Mn^II–Nb^IV Molecular Ferrimagnet

Iron(II)-octacyanoniobate(IV) ferromagnet with TC 43 K

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Influence of octacyanoniobate(IV)-bridging geometry on Tc in Mn2Nb ferrimagnets of identical 3D topology

Cited by 27 publications

References 50 publications

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(LMe2Ni−Ln){W(CN)8}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; LMe2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(LMe2Ni−Ln){W(CN)8}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; LMe2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

Self-Enhancement of Rotating Magnetocaloric Effect in Anisotropic Two-Dimensional (2D) Cyanido-Bridged MnII–NbIV Molecular Ferrimagnet

Iron(II)-octacyanoniobate(IV) ferromagnet with TC 43 K

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Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(L^Me2Ni−Ln){W(CN)₈}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L^Me2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

Hetero-Metallic {3d-4f-5d} Complexes: Preparation and Magnetic Behavior of Trinuclear [(L^Me2Ni−Ln){W(CN)₈}] Compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L^Me2 = Schiff base) and Variable SMM Characteristics for the Tb Derivative

Self-Enhancement of Rotating Magnetocaloric Effect in Anisotropic Two-Dimensional (2D) Cyanido-Bridged Mn^II–Nb^IV Molecular Ferrimagnet