A rare octacoordinated mononuclear iron(III) spin-crossover compound: synthesis, crystal structure and magnetic properties

2020 ◽  
Vol 76 (9) ◽  
pp. 856-862
Author(s):  
Xiaoyun Hao ◽  
Tong Cao ◽  
Yong Dou ◽  
Lu Yang ◽  
Zhen Zhou ◽  
...  

The chemistry of transition-metal complexes with unusually high coordination numbers has been of interest because of their application in catalytic and biological systems. Deprotonation of the ionogenic tetradentate ligand 6,6′-bis(1H-tetrazol-5-yl)-2,2′-bipyridine [H2bipy(ttr)2] in the presence of iron(III) and tetra-n-butylammonium bromide, [n-Bu4N]Br, in solution resulted in the synthesis of a rare octacoordinated anionic mononuclear complex, tetra-n-butylammonium bis[6,6′-bis(tetrazol-1-id-5-yl)-2,2′-bipyridine]iron(III) methanol hemisolvate dihydrate, (C16H36N)[Fe(C12H6N10)2]·0.5CH3OH·2H2O or [n-Bu4N][Fe{bipy(ttr)2}2]·0.5CH3OH·2H2O (1), which has been structurally characterized by elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. In 1, the coordination sphere of the iron(III) ion is a distorted bis-disphenoid dodecahedron, in which the eight coordination positions are occupied by eight N atoms from two independent tetradentate [bipy(ttr)2]2− anionic ligands, therefore forming the anionic [Fe{bipy(ttr)2}2]− unit, with the negative charge balanced by a free [n-Bu4N]+ cation. An investigation of the magnetic properties of 1 revealed a gradual incomplete spin-crossover behaviour below 150 K.

Molecules ◽  
2021 ◽  
Vol 26 (19) ◽  
pp. 6020
Author(s):  
Andrea Moneo-Corcuera ◽  
Breogán Pato-Doldan ◽  
Irene Sánchez-Molina ◽  
David Nieto-Castro ◽  
José Ramón Galán-Mascarós

Here we present the synthesis, structure and magnetic properties of complexes of general formula (Mn)(Me2NH2)4][Mn3(μ-L)6(H2O)6] and (Me2NH2)6[M3(μ-L)6(H2O)6] (M = CoII, NiII and CuII); L−2 = 4-(1,2,4-triazol-4-yl) ethanedisulfonate). The trinuclear polyanions were isolated as dimethylammonium salts, and their crystal structures determined by single crystal and powder X-ray diffraction data. The polyanionic part of these salts have the same molecular structure, which consists of a linear array of metal(II) ions linked by triple N1-N2-triazole bridges. In turn, the composition and crystal packing of the MnII salt differs from the rest of the complexes (with six dimethyl ammonia as countercations) in containing one Mn+2 and four dimethyl ammonia as countercations. Magnetic data indicate dominant intramolecular antiferromagnetic interactions stabilizing a paramagnetic ground state. Susceptibility data have been successfully modeled with a simple isotropic Hamiltonian for a centrosymmetric linear trimer, H = −2J (S1S2 + S2S3) with super-exchange parameters J = −0.4 K for MnII, −7.5 K for NiII and −45 K for CuII complex. The magnetic properties of these complexes and their easy processing opens unique possibilities for their incorporation as magnetic molecular probes into such hybrid materials as magnetic/conducting multifunctional materials or as dopant for organic conducting polymers.


Crystals ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 276 ◽  
Author(s):  
Tomoe Matsuyama ◽  
Keishi Nakata ◽  
Hiroaki Hagiwara ◽  
Taro Udagawa

A mononuclear iron(II) complex bearing the linear pentadentate N5 Schiff-base ligand containing two 1,2,3-triazole moieties and the MeCN monodentate ligand, [FeIIMeCN(L3-Me-3Ph)](BPh4)2·MeCN·H2O (1), have been prepared (L3-Me-3Ph = bis(N,N′-1-Phenyl-1H-1,2,3-triazol-4-yl-methylideneaminopropyl)methylamine). Variable-temperature magnetic susceptibility measurements revealed an incomplete one-step spin crossover (SCO) from the room-temperature low-spin (LS, S = 0) state to a mixture of the LS and high-spin (HS, S = 2) species at the higher temperature of around 400 K upon first heating, which is irreversible on the consecutive cooling mode. The magnetic modulation at around 400 K was induced by the crystal-to-amorphous transformation accompanied by the loss of lattice MeCN solvent, which was evident from powder X-ray diffraction (PXRD) studies and themogravimetry. The single-crystal X-ray diffraction studies showed that the complex is in the LS state (S = 0) between 296 and 387 K. In the crystal lattice, the complex-cations and B(1)Ph4− ions are alternately connected by intermolecular CH···π interactions between the methyl group of the MeCN ligand and phenyl groups of B(1)Ph4− ions, forming a 1D chain structure. The 1D chains are further connected by P4AE (parallel fourfold aryl embrace) interactions between two neighboring complex-cations, constructing a 2D extended structure. B(2)Ph4− ions and MeCN lattice solvents exist in the spaces of the 2D layer. DFT calculations verified that the 1,2,3-triazole-containing ligand L3-Me-3Ph gives a stronger ligand field around the octahedral coordination environment of the iron(II) ion than the analogous imidazole-containing ligand H2L2Me (= bis(N,N′-2-methylimidazol-4-yl-methylideneaminopropyl)methylamine) of the known compound [FeIIMeCN(H2L2Me)](BPh4)1.5·Cl0.5·0.5MeCN (2) reported by Matsumoto et al. (Nishi, K.; Fujinami, T.; Kitabayashi, A.; Matsumoto, N. Tetrameric spin crossover iron(II) complex constructed by imidazole⋯chloride hydrogen bonds. Inorg. Chem. Commun. 2011, 14, 1073–1076), resulting in the much higher spin transition temperature of 1 than that of 2.


1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.


2020 ◽  
Vol 43 (1) ◽  
pp. 26-42 ◽  
Author(s):  
Zahra Hajian Karahroudi ◽  
Kambiz Hedayati ◽  
Mojtaba Goodarzi

AbstractThis study presents a preparation of SrFe12O19– SrTiO3 nanocomposite synthesis via the green auto-combustion method. At first, SrFe12O19 nanoparticles were synthesized as a core and then, SrTiO3 nanoparticles were prepared as a shell for it to manufacture SrFe12O19–SrTiO3 nanocomposite. A novel sol-gel auto-combustion green synthesis method has been used with lemon juice as a capping agent. The prepared SrFe12O19–SrTiO3 nanocomposites were characterized by using several techniques to characterize their structural, morphological and magnetic properties. The crystal structures of the nanocomposite were investigated via X-ray diffraction (XRD). The morphology of SrFe12O19– SrTiO3 nanocomposite was studied by using a scanning electron microscope (SEM). The elemental composition of the materials was analyzed by an energy-dispersive X-ray (EDX). Magnetic properties and hysteresis loop of nanopowder were characterized via vibrating sample magnetometer (VSM) in the room temperature. Fourier transform infrared spectroscopy (FTIR) spectra of the samples showed the molecular bands of nanoparticles. Also, the photocatalytic behavior of nanocomposites has been checked by the degradation of azo dyes under irradiation of ultraviolet light.


2020 ◽  
Vol 10 (03) ◽  
pp. 2050003
Author(s):  
M. R. Hassan ◽  
M. T. Islam ◽  
M. N. I. Khan

In this research, influence of adding Li2CO3 (at 0%, 2%, 4%, 6%) on electrical and magnetic properties of [Formula: see text][Formula: see text]Fe2O4 (with 60% Ni and 40% Mg) ferrite has been studied. The samples are prepared by solid state reaction method and sintered at 1300∘C for 6[Formula: see text]h. X-ray diffraction (XRD) patterns show the samples belong to single-phase cubic structure without any impurity phase. The magnetic properties (saturation magnetization and coercivity) of the samples have been investigated by VSM and found that the higher concentration of Li2CO3 reduces the hysteresis loss. DC resistivity increases with Li2CO3 contents whereas it decreases initially and then becomes constant at lower value with temperature which indicates that the studied samples are semiconductor. The dielectric dispersion occurs at a low-frequency regime and the loss peaks are formed in a higher frequency regime, which are due to the presence of resonance between applied frequency and hopping frequency of charge carriers. Notably, the loss peaks are shifted to the lower frequency with Li2CO3 additions.


2014 ◽  
Vol 919-921 ◽  
pp. 2013-2016 ◽  
Author(s):  
Ya Bing Liu ◽  
Hong Jie Wang ◽  
Hong Kai Zhao

A POM - based organice - inorganic hybrid compound with the chemical formula of[Cu (phen)2]3[W6O19] (phen = 1,10-phenanthroline) (1) has been hydrothermally synthesized andstructurally characterized by the elemental analysis, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space groupC2/c witha=18.319(4) Å,b= 17.311(4) Å,c= 22.248(4) Å,β= 112.40(3) o,V= 6523(2) Å3,Z= 4, R1= 0.0448, andwR2=0.1218. Compound 1 consists of the [W6O19]3-building blocks and [Cu (phen)2]+metal organic cationic moieties, which are packed together via the extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. The adsorption of methylene blue (MB) under UV irradiation with 1 as the heterogeneous adsorbent has been investigated, showing a good adsorptive property of 1 for MB degradation.


2010 ◽  
Vol 654-656 ◽  
pp. 1106-1109
Author(s):  
Ya Qiong He ◽  
Chang Hui Mao ◽  
Jian Yang

Nanocrystalline Fe-Co alloy powders, which were prepared by high-energy mechanical milling, were nitrided under the mixing gas of NH3/H2 in the temperature range from 380°C to 510°C. X-ray diffraction (XRD) was used to analyze the grain size and reaction during the processing. The magnetic properties of the nitrided powders were measured by Vibrating Sample Magnetometer (VSM). The results show that with the appearance of Fe4N phase after nitride treatment, and the grain-size of FeCo phase decreases with the increase of nitridation temperature between 380°C to 450°C.The saturation magnetization of nitrided alloy powder treated at 480°C is about 18% higher than that of the initial Fe-Co alloy powder, accompanied by the reduction of the coercivity. Transmission electron microscope (TEM) was used, attempting to further analyze the effect of Fe4N phase on microstructure and magnetic properties of the powder mixtures.


2011 ◽  
Vol 268-270 ◽  
pp. 356-359 ◽  
Author(s):  
Wen Song Lin ◽  
C. H. Wen ◽  
Liang He

Mn, Fe doped ZnO powders (Zn0.95-xMnxFe0.05O2, x≤0.05) were synthesized by an ameliorated sol-gel method, using Zn(CH3COO)2, Mn(CH3COO)2and FeCl2as the raw materials, with the addition of vitamin C as a kind of chemical reducer. The resulting powder was subsequently compacted under pressure of 10 MPa at the temperature of 873K in vacuum. The crystal structure and magnetic properties of Zn0.95-xMnxFe0.05O2powder and bulk samples have been investigated by X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). X-ray photoelectron spectroscopy (XPS) was used to study chemical valence of manganese, iron and zinc in the samples. The x-ray diffraction (XRD) results showed that Zn0.95-xMnxFe0.05O (x≤0.05) samples were single phase with the ZnO-like wurtzite structure. No secondary phase was found in the XRD spectrum. X-ray photoelectron spectroscopy (XPS) showed that Fe and Mn existed in Zn0.95-xMnxFe0.05O2samples in Fe2+and Mn2+states. The results of VSM experiment proved the room temperature ferromagnetic properties (RTFP) of Mn, Fe co-doped ZnO samples.


2007 ◽  
Vol 130 ◽  
pp. 171-174 ◽  
Author(s):  
Z. Stokłosa ◽  
G. Badura ◽  
P. Kwapuliński ◽  
Józef Rasek ◽  
G. Haneczok ◽  
...  

The crystallization and optimization of magnetic properties effects in FeXSiB (X=Cu, V, Co, Zr, Nb) amorphous alloys were studied by applying X-ray diffraction methods, high resolution transmission electron microscopy (HRTEM), resistometric and magnetic measurements. The temperatures of the first and the second stage of crystallization, the 1h optimization annealing temperature and the Curie temperature were determined for different amorphous alloys. Activation energies of crystallization process were obtained by applying the Kissinger method. The influence of alloy additions on optimization effect and crystallization processes was carefully examined.


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