Search results for "spin crossover"

Cooperative Spin‐Crossover Behaviour in Polymeric 1D Fe II Coordination Compounds: [{Fe(tba) 3 }X 2 ]· n H 2 O

2007

A new family of 1D cooperative spin-crossover polymers with general formula [{Fe(tba)3}X2]·nH2O [tba = N-(4H-1,2,4-triazol-4-yl)benzamide; X = CF3SO3–, n = 2 (1), n = 0 (4); BF4–,n = 3 (2), n = 0 (5); 4-CH3C6H4SO3–, n = 3 (3), n = 0 (6)] has been synthesised and characterised using a series of spectroscopic methods, X-ray powder diffraction, magnetic susceptibility measurements and differential scanning calorimetry. The copper analogue of 1, [{Cu(tba)3}(CF3SO3)2]·3H2O (7), has also been synthesised and its crystal structure solved at 293 K. Compound 7 crystallises in the P space group. The bidentate N-(4H-1,2,4-triazol-4-yl)benzamide ligand bridges the copper ions through the 1,2-nitrogen p…

Cover Feature: Cyanido‐Bridged Fe II –M I Dimetallic Hofmann‐Like Spin‐Crossover Coordination Polymers Based on 2,6‐Naphthyridine (Eur. J. Inorg. Che…

2018

Crystal‐Structure Studies of Mononuclear Iron(II) Complexes with Two‐Step Spin Crossover: [Fe{5‐NO 2 ‐sal‐N(1,4,7,10)}] Revisited

2013

In the region of the spin transition of spin-crossover (SCO) compounds there coexist molecules in both high-spin (HS) and low-spin (LS) states. In the case of two-step spin transition, theoretical predictions and computer simulations have shown that HS and LS complex molecules should be ordered in the plateau region. Several examples that support this hypothesis are already presented in the literature. Herein, we discuss a mononuclear complex of iron(II) with two-step spin transition in terms of long-range ordering of HS and LS molecules. In such compounds, spin transition is associated with the formation of a superstructure. However, previous studies of the [Fe{5-NO2-sal-N(1,4,7,10)}] [5-N…

Temperature dependence of desolvation effects in hydrogen-bonded spin crossover complexes

2021

The synthesis, crystal structure and (photo)magnetic properties of the anhydrous spin crossover salt of formula [Fe(bpp)2](C6H8O4) (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; C6H8O4 = adipate dianion), obtained by desolvation at 400 K of the original tetrahydrate in a single-crystal-to-single-crystal (SC–SC) transformation, are reported. This work offers a comparison between this compound and the previously reported hydrated material ([Fe(bpp)2](C6H8O4)·4H2O, 1·4H2O), highlighting the significance of the thermal conditions used in the dehydration-rehydration processes. In both compounds, a hydrogen-bonded network between iron(II) complexes and adipate anions is observed. The original tetrahyd…

Synthesis, Structure and Properties of a Mixed Mononuclear/Dinuclear Iron(II) Spin-Crossover Compound with the Ligand 4-(p-Tolyl)-1,2,4-triazole

1999

A new iron(II) compound with the formula [Fe2(L)5(NCS)4]2[Fe(L)2(NCS)2(H2O)2] (I) [where L = 4-(p-tolyl)-1,2,4-triazole] has been synthesized and subjected to X-ray structure determination. Compound I crystallizes in the triclinic space group P–1 (no. 2) with a = 14.5785(11), b = 16.1253(11), c = 16.1963(8) A, α = 80.930(5), β = 85.796(5), γ = 78.132(6)°, V = 3676.2(4) A3. The structure refinement converged to wR2 = 0.172, RF = 0.084. The structure was found to consist of two types of iron-containing structural units, a mononuclear unit and a dinuclear one. The mononuclear unit has a crystallographic inversion centre, and is coordinated by two NCS anions, two triazole N1 nitrogen atoms, and…

2D and 3D bimetallic oxalate-based ferromagnets prepared by insertion of different FeIII spin crossover complexes

2010

The syntheses, structures and magnetic properties of the compounds of formula [Fe(III)(5-NO(2)sal(2)-trien)][Mn(II)Cr(III)(ox)(3)]·CH(3)NO(2).0.5H(2)O (1) and [Fe(III)(5-CH(3)Osal(2)-trien)][Mn(II)Cr(III)(ox)(3)] (2) are reported. The structure of 1, that crystallizes in the P2(1) chiral space group, presents a 2D honeycomb anionic layer formed by Mn(II) and Cr(III) ions linked through oxalate ligands and a cationic layer of [Fe(III)(5-NO(2)sal(2)-trien)](+) complexes intercalated between the 2D oxalate network. The structure of 2, that crystallizes in the Pna2(1) acentric space group, presents a 3D achiral anionic network formed by Mn(II) and Cr(III) ions linked through oxalate ligands wit…

Synthesis, Structure, and Magnetic Properties of a Tris[3-(2-pyridyl)-1,2,4-triazole]iron(II) Spin-Crossover Complex

2000

The synthesis and characterization of tris[3-(pyridin-2-yl)-1,2,4-triazole]iron(II) bis(tetrafluoroborate), obtained from the reaction of 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) and hexaaquairon(II) tetrafluoroborate, [Fe(H2O)6](BF4)2, is described, together with its crystal structures at two temperatures. X-ray crystallographic parameters are as follows: [Fe(Hpt)3](BF4)2·nH2O (n ≈ 2) at 250 K: orthorhombic space group Pbam, a = 15.8068(18) A, b = 17.2800(14) A, c = 21.215(2) A, V = 5794.7(10) A3, and Z = 8. [Fe(Hpt)3](BF4)2·nH2O (n ≈ 2) at 95 K: orthorhombic space group Pbam, a = 15.7080(12) A, b = 17.1023(16) A, c = 21.006(2) A, V = 5643.1(9) A3, and Z = 8. The FeII ions are (at both temper…

Insertion of a [Fe II (pyimH) 3 ] 2+ [pyimH = 2‐(1 H ‐Imidazol‐2‐yl)pyridine] Spin‐Crossover Complex Inside a Ferromagnetic Lattice Based on a Chiral…

2015

The insertion of the [FeII(pyimH)3]2+ [pyimH = 2-(1H-imidazol-2-yl)pyridine] spin-crossover complex into a ferromagnetic bimetallic oxalate network affords the hybrid compound [FeII(pyimH)3][MnIICrIII(ox)3]2·X (ox = C2O42–). This spin-crossover complex templates the growth of crystals formed by a chiral 3D oxalate network. The magnetic properties of this hybrid magnet show the coexistence of long-range ferromagnetic ordering at 4.5 K and a spin crossover of the intercalated [FeII(pyimH)3]2+ complex above 250 K. The compound presents a light-induced excited spin-state trapping (LIESST) effect below 60 K although with limited photoconversion (less than 8 %).

Intersystem Crossing and Light-Induced Bistability in Iron(?) Spin-Crossover Compounds

1996

Abstract The dynamics of the high-spin→low-spin intersystem crossing process in iron(?) spin-crossover compounds are strongly influenced by cooperative effects of elastic origin which are due to the large difference in volume between high-spin and low-spin complexes. The deviation from first order kinetics is attributed to a build-up of an internal pressure as the relaxation proceeds, leading to a characteristic self-acceleration. The elastic interactions may lead to a light-induced bistability for systems which otherwise remain in the high-spin state down to cryogenic temperatures.

Mössbauer effect study of the electronic ground state of iron(II) in [57FexM1−x(bipy)3](ClO4)2 (M = Mn, Ni, Zn) and [57FexM1−x(phen)3](ClO4)2 (M = Ni…

1980

Earlier work in our laboratory on the effect of metal dilution on the 5T2(Oh ⇌ 1A1(Oh) equilibrium in polycrystalline spin crossover systems of iron(II) has shown that the relative stability of the high spin state, 5T2(Oh), at a given temperature, increases markedly with decreasing iron concentration. These results have initiated the present work. Using 57Fe Mossbauer spectroscopy, we have investigated the electronic ground state of iron(II) in the highly diluted solid solutions [FexM1−xL3] with L = bipy, M = Mn, Ni, Zn, x ≲ 0.005 and L = phen, M = Ni, Zn, x ≲ 0.005. Although the critical field potential (Vc) of the pure iron complexes, which are known to be low spin, is reported to be not …