Search Results (22)

Two iron(III) spin crossover complexes [Fe(⁵Cl-L)(NCS)] (1) and [Fe(⁵Cl-L)(NCSe)] (2) were synthesized with the pentadentate Schiff base ligand ⁵Cl-L and thiocyanato and selenocyanato as coligands. ⁵Cl-L, as an asymmetric {N₃O₂} donor Schiff base, was synthesized by a condensation reaction of 5-chlorosalicyladehyde using the asymmetric N-(2-aminoethyl)-1,3-propanediamine. The complexes exhibited a spin crossover at 280 (1) and 293 K (2), respectively, and were subjected to electron spin resonance (ESR) and Mössbauer spectroscopy at 77, 295 and 325 K. Ab initio CASSCF calculations followed by the NEVPT2 method were applied for predicting the g-tensor components as well as Mössbauer parameters. Full article

A series of mononuclear complexes, [Fe(L5)(bylim)](BPh₄), where L5 represents a pentadentate Schiff base ligand, bylim is 1-benzyl-1-imidazole, and BPh₄⁻ is the tetraphenylborate anion, was synthesized. The determined crystal structures indicate the absence of significant cooperative interactions, which influence the properties of the eventual spin transition. Changes in magnetic behavior induced by substitution of the pentadentate ligand were investigated through magnetic susceptibility measurements. It was found that only complexes containing a non-substituted secondary amino group exhibit some form of spin crossover, whereas the majority of those with a methyl substituent remain in the high-spin state across the entire measured temperature range (2–300 K). The changes induced by the substitution of the secondary amine group were further explored through theoretical calculations at DFT and CASSCF/NEVPT2 levels of theory. The topology and energetics of electron density and atomic charges were investigated through QT-AIM calculations. Full article

To investigate the halogen substitution effect on the anionic spin crossover (SCO) complexes, azobisphenolate ligands with 5,5′-dihalogen substituents from fluorine to iodine were synthesized, and their anionic Fe^III complexes 1F, 1Cl, 1Br, and 1I were isolated. The temperature dependence of magnetic susceptibility and crystal structure revealed that 1F, 1Cl, and 1Br are all isostructural and exhibit SCO with the rotational motion of the cation and ligands, whereas 1I shows incomplete SCO. Note that 1Cl and 1Br showed irreversible and reversible cooperative SCO transitions, respectively. Short intermolecular contacts between the Fe^III complex anions were found despite Coulomb repulsions for all the complexes. The topological analysis of the electron density distributions revealed the existence of X···X halogen bonds, C–H···X, C–H···N, and C–H···O hydrogen bonds, and C–H···π interactions are evident. The dimensionality of intermolecular interactions is suggested to be responsible for the cooperative SCO transitions in 1Cl and 1Br, whereas the disorder due to the freezing of ligand rotations in 1Cl is revealed to inhibit the SCO cooperativity. Full article

New iron(II) complexes with 2,6-bis(1H-imidazol-2-yl)-4-methoxypyridine (L) of the composition [FeL₂]A_n∙mH₂O (A = SO₄²⁻, n = 1, m = 2 (I); A = ReO₄⁻, n = 2, m = 1 (II); A = Br⁻, n = 2, m = 2 (III)) have been synthesized and investigated. To determine the coordination ability of the ligand, a single crystal of a copper(II) complex of the composition [CuLCl₂] (IV) was obtained and studied by X-ray technique. Compounds I–III were studied using methods of X-ray phase analysis, electron (diffuse reflection spectra), infrared and Mössbauer spectroscopy, static magnetic susceptibility. The study of the µ_eff(T) dependence showed that the ¹A₁ ↔ ⁵T₂ spin crossover manifests itself in the compounds. The spin crossover is accompanied by thermochromism: there is a distinct color change orange ↔ red-violet. Full article

This paper focuses on the synthesis, structural characterization, and study of the optical, magnetic, and thermal properties of novel architectures combining metal ions as magnetoactive centers and photoactive blocks formed by carbazole units. For this purpose, a series of azomethine complexes of the composition [Fe(L)₂]X (L = 3,6-bis[(3′,6′-di-tert-butyl-9-carbazol)-9-carbazol]benzoyloxy-4-salicylidene-N′-ethyl-N-ethylenediamine, X = NO₃⁻, Cl⁻, PF₆⁻) were synthesized by the reaction of metal salts with Schiff bases in a mixture of solvents. The UV–Vis absorption properties were studied in dichloromethane and rationalized via time-dependent density functional theory (DFT) calculations. Upon excitation at 350 nm, the compounds exhibited an intense dual fluorescence with two emission bands centered at ~445 and ~485 nm, which were assigned to π_carb–π* intraligand and π_carb–d_Fe ligand-to-metal charge-transfer excited states. EPR spectroscopy and SQUID magnetometry revealed solid-state partial spin crossover in some compounds, and antiferromagnetic interactions between the neighboring Fe(III) ions. Full article

In this mini-review of our research group’s activity, the application of ⁵⁷Fe Mössbauer spectroscopy in studies of electronic structure, coordination environment, and magnetic interactions in an interesting series of Fe(II/III) compounds selected is discussed. We selected two prominent phenomena that arose during investigations of selected groups of compounds carried out at different periods of time: (1) very high magnetic hyperfine fields observed at low temperatures; (2) changes in the oxidation state of the central iron atom of complexes in the solid state during interactions with gaseous O₂/H₂O mixtures, resulting in spin crossover (SCO). Full article

In this study, crystals of the hybrid layered structure, combined with Fe(III) Spin-Crossover (SCO) complexes with metal-dithiolate anionic radicals, and the precursors with nitrate and iodine counterions, are obtained and characterized. [Fe(III)(3-OMe-Sal₂trien)][Ni(dmit)₂] (1), [Fe(III)(3-OMe-Sal₂trien)]NO₃·H₂O (2), [Fe(III)(3-OMe-Sal₂trien)]I (3) (3-OMe-Sal₂trien = hexadentate N₄O₂ Schiff base is the product of the condensation of triethylenetetramine with 3-methoxysalicylaldehyde; H₂dmit = 2-thioxo-1,3-dithiole-4,5-dithiol). Bulk SCO transition was not achieved in the range 2.0–350 K for all three compounds. Alternatively, the hybrid system (1) exhibited irreversible segregation into the spatial fractions of Low-Spin (LS) and High-Spin (HS) phases of the ferric moiety, induced by thermal cycling. Fractioning was studied using both SQUID and EPR methods. Magnetic properties of the LS and HS phases were analyzed in the framework of cooperative interactions with anionic sublattice: Anion radical layers Ni(dmit)₂ (1), and H-bonded chains with NO₃ and I (2,3). LS phase of (1) exhibited unusual quasi-two-dimensional conductivity related to the Arrhenius mechanism in the anion radical layers, ρ_||c = 2 × 10⁵ Ohm·cm and ρ_⊥c = 7 × 10² Ohm·cm at 293 K. Ground spin state of the insulating HS phase was distinctive by ferromagnetically coupled spin pairs of HS Fe³⁺, S = 5/2, and metal-dithiolate radicals, S = 1/2. Full article

Herein, the syntheses, solid-state molecular structures, and characterization of two types of one-dimensional Fe^III coordination polymers showing thermally induced spin crossover are reported. The reaction of [Fe(acen)Cl] (acen²⁻ = N,N′-ethylenebis(acetylacetonylideneaminate) with 3,3′-bpy or 4,4′-bpy (bpy = bipyridine) produced zigzag and linear one-dimensional chain complexes, [Fe(acen)(3,3′-bpy)][BPh₄] (1) or [NEt₃H][Fe(acen)(4,4′-bpy)][BPh₄]₂·0.5(4,4′-bpy) (2), respectively, as confirmed by single crystal X-ray diffraction analysis. Variable-temperature single crystal X-ray diffraction measurements, continuous-wave X-band electron paramagnetic resonance (EPR) spectra, ⁵⁷Fe Mössßauer spectra, and DC magnetic susceptibility data revealed that complex 1 exhibited a gradual and complete spin crossover at a transition temperature of 212 K, while complex 2 undergoes an incomplete spin crossover even at 400 K. Full article

A review of the tripodal Schiff base (SB) complexes of tris(2-aminoethyl)amine, N_ap(CH₂CH ₂NH₂)₃ (tren), and a few closely related tripodal amines with Cr(II), Mn(III) (d⁴), Mn(II), Fe(III) (d⁵), Fe(II) (d⁶), and Co(II) (d⁷) is provided. Attention is focused on examination of key structural features, the M-N_imine, M-N_amine, or M-O and M-N_ap bond distances and N_imine-M-N(O) bite and C-N_ap-C angles and how these values correlate with spin state selection and spin crossover (SCO) behavior. A comparison of these experimental values with density functional theory calculated values is also given. The greatest number, 132, of complexes is observed with cationic mononuclear iron(II) in a N₆ donor set, Fe(II)N₆. The dominance of two spin states, high spin (HS) and low spin (LS), in these systems is indicated by the bimodal distribution of histogram plots of Fe(II)-N_imine and Fe(II)-N_{azole/pyridine} bond distances and of N_imine–Fe(II)-N_{azole/pyridine} and C-N_ap-C bond angles. The values of the two maxima, corresponding to LS and HS states, in each of these histograms agree closely with the theoretical values. The iron(II)-N_imine and iron(II)-N_{azole/pyridine} bond distances correlate well for these complexes. Examples of SCO complexes of this type are tabulated and a few of the 20 examples are discussed that exhibit interesting features. There are only a few mononuclear iron(III) cationic complexes and one is SCO. In addition, a significant number of supramolecular complexes of these ligands that exhibit SCO, intervalence, and chiral recognition are discussed. A summary is made regarding the current state of this area of research and possible new avenues to explore based on analysis of the present data. Full article

Spin crossover in transition metal complexes can be studied in great detail with computational chemistry. Over the years, the understanding has grown that the relative stability of high-spin (HS) versus low-spin (LS) states is a subtle balance of many factors that all need to be taken into account for a reliable description. Among the different contributions, the zero-point energy (ZPE) and the entropy play key roles. These quantities are usually calculated assuming a harmonic oscillator model for the molecular vibrations. We investigated the impact of including anharmonic corrections on the ZPE and the entropy and indirectly on the critical temperature of spin crossover. As test systems, we used a set of ten Fe(II) complexes and one Fe(III) complex, covering different coordination modes (mono-, bi-, and tri-dentate ligands), decreasing coordination number upon spin crossover, coordination by second- and third-row atoms, and changes in the oxidation state. The results show that the anharmonicity has a measurable effect, but it is in general rather small, and tendencies are not easily recognized. As a conclusion, we put forward that for high precision results, one should be aware of the anharmonic effects, but as long as computational chemistry is still struggling with other larger factors like the influence of the environment and the accurate determination of the electronic energy difference between HS and LS, the anharmonicity of the vibrational modes is a minor concern. Full article

A new family of mixed valent, double salt spin crossover compounds containing anionic Fe^III and cationic Fe^II compounds i.e., [Fe^II{(pz)₃CH}₂][Fe^III(azp)₂]₂·2H₂O (4), [Fe^II(TPPZ)₂][Fe^III(azp)₂]₂]·H₂O (5) and [Fe^II(TPPZ)₂][Fe^III(azp)₂]₂]·H₂O·3MeCN (6) (where (pz)₃CH = tris-pyrazolylmethane, TPPZ = 2,3,5,6, tetrapyridylpyrazine and azp²⁻ = azadiphenolato) has been synthesized and characterised. This is the first time that the rare anionic spin crossover species, [Fe^III(azp)₂]⁻, has been used as an anionic component in double salts complexes. Single crystal structures and magnetic studies showed that compound 6 exhibits a spin transition relating to one of the Fe^III centres of the constituent Fe^II and Fe^III sites. Crystal structures of the anionic and cationic precursor complexes were also analysed and compared to the double salt products thus providing a clearer picture for future crystal design in double spin crossover materials. We discuss the effects that the solvent and counterion had on the crystal packing and spin crossover properties. Full article

We report on the vacuum thermal deposition of bilayer thin films of the luminescent complex Ir(ppy)₃, tris[2-phenylpyridinato-C2,N]iridium(III), and the spin crossover complex [Fe(HB(tz)₃)₂], bis[hydrotris(1,2,4-triazol-1-yl)borate]iron(II). Switching the spin state of iron ions from the low spin to the high spin state around 337 K leads to a reversible jump of the luminescence intensity, while the spectrum shape and the luminescence lifetime remain unchanged. The luminescence modulation occurs due to the different UV light absorption properties of the iron complex in the two spin states and its magnitude can therefore be precisely adjusted by varying the film thickness. These multilayer luminescence switches hold potential for micro- and nanoscale thermal sensing and imaging applications. Full article

New Fe(III) compounds from qsal ligand, [Fe(qsal)₂](CH₃OSO₃) (1) and [Fe(qsal)₂](CH₃SO₃)·CH₃OH (3), along with known compound, [Fe(qsal)₂](CF₃SO₃) (2), were obtained as large well-shaped crystals (Hqsal = N-(8-quinolyl)salicylaldimine). The compounds 1 and 2 were in the low-spin (LS) state at 300 K and exhibited a cooperative spin crossover (SCO) transition with a thermal hysteresis loop at higher temperatures, whereas 3 was in the high-spin (HS) state below 300 K. The optical conductivity spectra for 1 and 3 were calculated from the single-crystal reflection spectra, which were, to the best of our knowledge, the first optical conductivity spectra of SCO compounds. The absorption bands for the LS and HS [Fe(qsal)₂] cations were assigned by time-dependent density functional theory calculations. The crystal structures of 1 and 2 consisted of a common one-dimensional (1D) array of the [Fe(qsal)₂] cation, whereas that of 3 had an unusual 1D arrangement by π-stacking interactions which has never been reported. The crystal structures in the high-temperature phases for 1 and 2 indicate that large structural changes were triggered by the motion of counter anions. The comparison of the crystal structures of the known [Fe(qsal)₂] compounds suggests the significant role of a large non-spherical counter-anion or solvate molecule for the total lattice energy gain in the crystal of a charged complex. Full article

Structural and magnetic data on two iron (III) complexes with a hexadentate Schiff base chelating ligand and Cl⁻ or BPh₄⁻ counterions are reported. In the solid state, the Cl⁻ complex [Fe(5F-sal₂333)]Cl, 1, is high spin between 5–300 K while the BPh₄⁻ analogue [Fe(5F-sal₂333)]BPh₄, 2, is low spin between 5–250 K, with onset of a gradual and incomplete spin crossover on warming to room temperature. Structural investigation reveals different orientations of the hydrogen atoms on the secondary amine donors in the two salts of the [Fe(5F-sal₂333)]⁺ cation: high spin complex [Fe(5F-sal₂333)]Cl, 1, crystallizes with non-meso orientations while the spin crossover complex [Fe(5F-sal₂333)]BPh₄, 2, crystallizes with a combination of meso and non-meso orientations disordered over one crystallographic site. Variable temperature electronic absorption spectroscopy of methanolic solutions of 1 and 2 suggests that both are capable of spin state switching in the solution. Full article

Hybrid ion-pair crystals involving hexadentate [Fe(III)(3-OMesal₂-trien)]⁺ spin-crossover (SCO) cationic complexes and anionic gold complexes [Au(dmit)₂]⁻ (1) (dmit = 4,5-dithiolato-1,3-dithiole-2-thione) and [Au(dddt)₂]⁻ (2) (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate) were synthesized and studied by single-crystal X-ray diffraction, P-XRD, and SQUID magnetometry. Our study shows that both complexes have similar 1:1 stoichiometry but different symmetry and crystal packing. Complex 1 has a rigid structure in which the SCO cations are engaged in strong π-interplay with molecular surrounding and does not show SCO transition while 2 demonstrates a reversible transition at T_sco = 118 K in a much “softer”, hydrogen-bonded structure. A new structural indicator of spin state in [Fe(sal₂-trien)]⁺ complexes based on conformational analysis has been proposed. Aging and thermocycling ruined the SCO transition increasing the residual HS fraction from 14 to 41%. Magnetic response of 1 is explained by the AFM coupled dimers S = 5/2 with J₁ = −0.18 cm⁻¹. Residual high-spin fraction of 2, apart from a contribution of the weak dimers with J₁₂ = J₃₄ = −0.29 cm⁻¹, is characterized by a stronger interdimer coupling of J₂₃ = −1.69 cm⁻¹, which is discussed in terms of possible involvement of neutral radicals [Au(dddt)₂]. Full article