4119-52-2

Usage

Chemical Properties

cub red crystal(s); deliquescent; decomposes on heating [MER06] [CRC10]

Preparation

Though the simple cyanide Fe(CN)3 is unknown, the thiocyanate is prepared as dark violet crystals by reaction of thiocyanogen with iron or by extracting a mixture of potassium thiocyanate and an iron(III) salt with ether, followed by evaporation of the ether. It is very soluble in water from which it crystallizes as the red trihydrate Fe(SCN)3. 3H2O. The blood-red colour developed when dilute solutions of iron(III) salts and thiocyanate ions are mixed is due largely to the [Fe(SCN(H2O)5]2+ ion; this reaction finds extensive use in the qualitative and quantitative determination of iron.

InChI:InChI=1/3CHNS.Fe/c3*2-1-3;/h3*3H;/q;;;+3/p-3

Upstream product

• 333-20-0 potassium thioacyanate 
• 2092-17-3 barium thiocyanate 
• 1701-93-5 silver thiocyanate 
• 7705-08-0 iron(III) chloride 
• 19229-76-6 iron(III) 
• 15192-76-4 copper(II) thiocyanate 
• 7439-89-6 iron 
• 1111-67-7 copper(I) thiocyanate 
• 463-56-9 thiocyanic acid 
• 592-85-8 mercury(II) thiocyanate 
• 4119-52-2 iron(III) thiocyanate 
• 767234-62-8 iron(II) carbonate 
• 3129-90-6 isothiocyanic acid 
• 7704-34-9 sulfur 

Downstream Products

• 61406-88-0 2-Methylcyclohexylthiocyanat 
• 61406-91-5 1,2-Dimethylcyclohexylthiocyanat 
• 463-56-9 thiocyanic acid 
• 124-38-9 carbon dioxide 
• 7664-93-9 sulfuric acid 
• 7553-56-2 iodine 
• 540-72-7 sodium thiocyanide 
• 460-19-5 ethanedinitrile 
• 74-90-8 hydrogen cyanide 
• 7783-06-4 hydrogen sulfide 
• 7664-41-7 ammonia 
• 64-19-7 acetic acid 
• 7439-89-6 iron 
• 7704-34-9 sulfur 

Relevant academic research and scientific papers

Coordination-driven self-assembly of a series of dinuclear M2L2mesocates with a bis-bidentate pyridylimine ligand

Four isostructural dinuclear M2L2mesocates of the general formula [M2(NCS)4(L)2]·4.5MeOH (1M; M = Mn, Fe, Co, Zn) were constructed by using the coordination-driven self-assembly of the [M(NCS)2] precursor and the flexible bis-bidentate pyridylimine Schiff base ligand L (L = 4,4′-(1,4-phenylenebis(oxy))bis(N-(pyridin-2-ylmethylene)aniline). The centrosymmetric M2L2mesocate forms through the side-by-side coordination of two L ligands to a pair of M(ii) ions. The mesocates exhibit a reversible temperature induced desolvation-solvation behavior without losing their structural integrity. The activated1Co, as the representative M2L2mesocate, shows an exceptionally high MeOH vapour uptake capacity of 481.9 cm3g?1(68.8 wt%) at STP with good recyclability. Notably, it also exhibits CO2adsorption with an uptake capacity of 20.2 cm3g?1(3.6 wt%) at room temperature and 1 bar.

Highly Ordered, Self-Assembled Monolayers of a Spin-Crossover Complex with In-Plane Interactions

For the technological integration of molecular switches in electronic devices, self-assembling nanomaterials of such switches are highly sought after. The syntheses of a new tetrapyridyl ligand bearing a C12 alkyl chain and two N?H bridges (compound 1) and of its iron(II) complex [Fe(1)(NCS)2] (compound 2), are described. Magnetic susceptibility data for bulk samples of 2 confirmed their gradual spin-crossover properties. The self-assembly of 1 and 2 on highly ordered pyrolytic graphite surfaces (HOPG) was investigated by Scanning Tunneling Microscopy (STM). Both compounds 1 and 2 formed ordered monolayers after deposition by drop casting. The patterns of the two compounds are very different, which is attributed to the fundamentally different hydrogen bonding networks before and after coordination of Fe(NCS)2 to the tetradentate chelate. Two possible models for the self-assembly of 1 and 2 are provided. This work suggests that it is possible to design molecular switches that self-assemble on surfaces in highly ordered monolayer films. This is a significant step in the development of spin-switching materials, which may streamline the integration of molecular switches in for example memory and sensing devices.

Tuning of crystallization method and ligand conformation to give a mononuclear compound or twodimensional SCO coordination polymer based on a new semi-rigid V-shaped bis-pyridyl bis-amide ligand

With the new semi-rigid V-shaped bidentate pyridyl amide compound 5-methyl- N,N0-bis(pyridin-4-yl)benzene-1,3-dicarboxamide (L) as an auxiliary ligand and the FeII ion as the metal centre, one mononuclear complex, bis(methanol-O)bis[5- methyl-N,N0-bis(pyridin-4-yl)benzene-1,3-dicarboxamide-N]bis(thiocyanato-N)- iron(II), [Fe(SCN)2(C19H16N4O2)2(CH3OH)2] (1), and one two-dimensional coordination polymer, catena-poly[[[bis(thiocyanato-N)iron(II)]-bis[-5-methyl- N,N0-bis(pyridin-4-yl)benzene-1,3-dicarboxamide-2N:N0]] methanol disolvate dihydrate], {[Fe(SCN)2(C19H16N4O2)2]2CH3OH2H2O}n (2), were prepared by slow evaporation and H-tube diffusion methods, respectively, indicating the effect of the method of crystallization on the structure type of the target product. Both complexes have been structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray crystallography. The singlecrystal X-ray diffraction analysis shows that L functions as a monodentate ligand in mononuclear 1, while it coordinates in a bidentate manner to two independent Fe(SCN)2 units in complex 2, with a different conformation from that in 1 and the ligands point in two almost orthogonal directions, therefore leading to a two-dimensional grid-like network. Investigation of the magnetic properties reveals the always high-spin state of the FeII centre over the whole temperature range in 1 and a gradual thermally-induced incomplete spin crossover (SCO) behaviour below 150 K in 2, demonstrating the influence of the different coordination fields on the spin properties of the metal ions. The current results provide useful information for the rational design of functional complexes with different structure dimensionalities by employing different conformations of the ligand and different crystallization methods.

Strengthening the Magnetic Interactions in Pseudobinary First-Row Transition Metal Thiocyanates, M(NCS)2

Understanding the effect of chemical composition on the strength of magnetic interactions is key to the design of magnets with high operating temperatures. The magnetic divalent first-row transition metal (TM) thiocyanates are a class of chemically simple layered molecular frameworks. Here, we report two new members of the family, manganese(II) thiocyanate, Mn(NCS)2, and iron(II) thiocyanate, Fe(NCS)2. Using magnetic susceptibility measurements on these materials and on cobalt(II) thiocyanate and nickel(II) thiocyanate, Co(NCS)2 and Ni(NCS)2, respectively, we identify significantly stronger net antiferromagnetic interactions between the earlier TM ions-a decrease in the Weiss constant, θ, from 29 K for Ni(NCS)2 to-115 K for Mn(NCS)2-a consequence of more diffuse 3d orbitals, increased orbital overlap, and increasing numbers of unpaired t2g electrons. We elucidate the magnetic structures of these materials: Mn(NCS)2, Fe(NCS)2, and Co(NCS)2 order into the same antiferromagnetic commensurate ground state, while Ni(NCS)2 adopts a ground state structure consisting of ferromagnetically ordered layers stacked antiferromagnetically. We show that significantly stronger exchange interactions can be realized in these thiocyanate frameworks by using earlier TMs.

A thermal- and light-induced switchable one-dimensional rare loop-like spin crossover coordination polymer

Rare loop-like isostructural one-dimensional coordination polymer (1D-CP) systems formulated as {Fe(DPIP)2(NCSe)2}n·4DMF (1) and {Fe(DPIP)2(NCSe)2}n·4DMF (2) were obtained by self-assembling FeII and pseudohalide NCX-(X = S, Se) ions in presence of the V-shaped bidentate bridging ligand, namely, N,N′-dipyridin-4-ylisophthalamide (DPIP), and were characterized by elemental analysis, IR spectroscopy, TGA, single crystal X-ray diffraction and powder X-ray diffraction. The magnetic studies show that complex 2 undergoes a complete thermally induced spin crossover (SCO) behavior centered at T1/2 = 120 K with ca. 5 K thermal hysteresis loop and light-induced excited spin state trapping effect (LIESST) with TLIESST = 65 K. However, either the homologous X = S (1) or the desolvated form of complex 2 is high spin at all temperatures, proving further the concerted synergy for the SCO of 2 between the intrinsic ligand field and that indirectly induced via hydrogen bond interaction. The current results provide valuable information for the design of new 1D SCO systems via the rational control of the cooperated effects derived from the intramolecular coordination bond and the intermolecular supramolecular interactions.

Mono- and heteroligand iron(II) complexes with tris(3,5-dimethylpyrazol-1-yl)methane

Coordination compounds of iron(II) thiocyanate with tris(3,5-dimethylpyrazol-1-yl)methane (HC(3,5-Me2Pz)3), [Fe(HC(3,5-Me2Pz)3)2](NCS)2] (I) and [Fe(HC(3,5-Me2Pz)3)(Рhz)(NCS)2] · H2O (II), where Рhz is phthalazine, are synthesized. The complexes are studied by X-ray diffraction analysis, diffuse reflectance and IR spectroscopy, and static magnetic susceptibility measurements. The single crystals are obtained, and the molecular and crystal structures of complex II and compounds [Fe(HC(3,5-Me2Pz)3)(3,5-Me2Pz)(NCS)2] · С2H5OH (III), where 3,5-Me2Pz is 3,5-dimethylpyrazole, and [Fe(HC(3,5-Me2Pz)3)2][Fe(HC(3,5-Me2Pz)3)(NCS)3]2 (IV) are determined (CIF files CCDC 1415452 (II), 1415453 (III), and 1415454 (IV)). The study of the temperature dependence μeff(Т) in a range of 2–300 K shows exchange interactions of the antiferromagnetic character between the iron(II) ions in complexes I and II.

Structures and spin states of crystalline [Fe(NCS)2L2] and [FeL3]2+ complexes (L = an annelated 1,10-phenanthroline derivative)

The phase behaviour and spin states of [Fe(NCS)2(dpq)2] (1; dpq = dipyrido[3,2-f:2′,3′-h]quinoxaline), [Fe(NCS)2(dppz)2] (2; dppz = dipyrido[3,2-a:2′3′-c]phenazine) and [Fe(NCS)2(dppn)2] (3; dppn = dipyrido[3,2-a:2′3′-c]benzophenazine) have been investigated. Solvent-free 1 and 2 are isostructural and low-spin in the crystalline state, in contrast to previously published 2·py (py = pyridine) which exhibits a hysteretic spin-crossover (SCO) transition near 140 K. The inactivity of 1 and 2 towards SCO may relate to their more crowded intermolecular lattice environment, particularly two very short intermolecular anion?π contacts involving the NCS- ligands. Two solvate phases of 1 are also described, including 1·2py which undergoes gradual SCO with T1/2 ca. 188 K. Bulk samples of 2 and 3 are predominantly low-spin and isostructural with the crystals of 2 by powder diffraction, but bulk samples of 1 contain an extra phase that exhibits hysteretic SCO, but was not crystallographically characterised. Crystal structures of low-spin [Fe(dppz)3][ClO4]2 (4) and a solvate of [Fe(dppn)3][BF4]2 (5) are also described, which are the first homoleptic complexes of these ligands to be crystallographically characterised.

Stabilization of the Low-Spin State in a Mononuclear Iron(II) Complex and High-Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding

The tetrapyridyl ligand bbpya (bbpya=N,N-bis(2,2′-bipyrid-6-yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)2] (1) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai's domain model, and powder X-ray diffraction measurements, 1 is low-spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong N-H?S intermolecular H-bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1. DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N'-di(pyrid-2-yl)-2,2′-bipyridine-6,6′-diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)(NCS)2] (2). Periodic DFT calculations suggest that crystal-packing effects are significant for compound 2, in which they destabilize the HS state by about 1500 cm-1. The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing.

Structure and magnetic properties of an unusual homoleptic iron(iii) thiocyanate dimer

We describe the structural and variable temperature magnetic susceptibility properties of an unusual homoleptic bimetallic iron(iii) thiocyanate tetraanion. This work represents the first structurally characterized bis(μ-1,3-thiocyanato) dimer of iron(iii). A weak antiferromagnetic exchange interaction is observed between the two iron(iii) ions, which is supported by broken symmetry density functional theory (DFT) calculations.

Coligand and solvent effects on the architectures and spin-crossover properties of (4,4)-connected iron(II) coordination polymers

The self-assemblies of 1,4-bis(pyrid-4-yl)benzene (bpb) and Fe(NCX)2 (X = S, Se, BH3) afforded six coordination polymers with the general formula of [Fe(bpb)2(NCX)2]·Y (X = S and Y = 3C2H5OH·2.5H2O for complex 4, X = S and Y = 2C2H5OH for 5, X = Se and Y = 2C2H5OH·H2O for 6, X = Se and Y = 0.67CH2Cl2·1.33C2H5OH·0.67H2O for 7, X = BH3 and Y = 3C2H5OH·2H2O for 8, X = BH3 and Y = 2CH2Cl2·2C2H5OH for 9). The frameworks of complexes 4 and 5 with the NCS- anion as coligand are supramolecular isomers, of which complex 4 features a threefold self-interpenetrated three-dimensional (3D) CdSO4-type topological structure with a Schl?fli symbol of 65·8, and complex 5 is a two-dimensional (2D) 44 rhombic grid network. These two complexes are purely high-spin systems. Complexes 6 and 7 with the NCSe- anion as coligand, both having the 3D 65·8 CdSO4-type framework, show gradual and incomplete spin-crossover behaviors with transition temperature T1/2 being equal to 86 and 96 K, respectively. The usage of NCBH3- anion as coligand leads to the formation of 2D 44 rhombic grid networks for both complexes 8 and 9, which undergo relatively abrupt, complete spin crossover with T1/2 being equal to 247 and 189 K, respectively. The structural divergences are attributed to the coligands NCX- (X = S, Se, BH3) and solvent molecules. Meanwhile, a significant coligand effect is observed on the spin-crossover behaviors of these complexes, and the completeness and transition temperature of spin-state conversion depends on the nature of the coligand, that is, T1/2(NCS-) 1/2(NCSe-) 1/2(NCBH3-). These results further facilitate the design and synthesis of spin-crossover complexes with spin-state conversion.