新型"分子合金"类Fe(II)配合物的合成和自旋转换性能

合成了Fe[(Htrz)~9~/~4(NH~2trz)~3~/~4](BF~4)~2.H~2O(1)和Fe[(Htrz)~3~/~2(NH~2trz)](BF~4).3H~2O(2)两个"分子合金"类自旋转换配合物。其变温光谱表明,它们在室温附近具有自旋转换行为,同时还伴有热致变色及滞后现象。     

新型"分子合金"类Fe(II)配合物的合成和自旋转换性能

合成了Fe[(Htrz)~9~/~4(NH~2trz)~3~/~4](BF~4)~2.H~2O(1)和Fe[(Htrz)~3~/~2(NH~2trz)](BF~4).3H~2O(2)两个"分子合金"类自旋转换配合物。其变温光谱表明,它们在室温附近具有自旋转换行为,同时还伴有热致变色及滞后现象。     

Electronic and spatial structure of spin transition iron(II) tris(4-amino-1,2,4-triazole) nitrate and perchlorate complexes

Electronic and spatial structure of polynuclear iron(II) complexes Fe(ATr)₃(ClO₄)₂, Fe(ATr)₃(NO₃)₂, and Fe_0.34Zn_0.66(ATr)₃(NO₃)₂ (where ATr is 4-amino-1,2,4-triazole) is investigated using EXAFS and XANES spectroscopy and X-ray fluorescent spectroscopy. Changes in the distances to the first four coordination spheres of Fe and Zn atoms upon spin transitions induced by variations of the anion or temperature are analyzed. It is shown that in polynuclear complexes the spin transition (from S=2 to S=0) is accompanied by pronounced variations in the electronic and spatial structure. A mutual effect of Fe and Zn atoms was found which alters the local environment of the low-spin Fe atoms in a magnetically diluted complex as compared to the initial one. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 4, pp. 96–104, July–August, 1994. Translated by L. Smolina     

EXAFS study of binuclear hydroxo-bridged copper(II) complexes

Extended X-ray absorption fine structure (EXAFS) measurements have been recorded at the K-edge of copper in binuclear monohydroxo-bridged copper(II) complexes [(bpy)₂Cu–OH–Cu(bpy)₂](ClO₄)₃ (1) and [(phen)₂Cu–OH–Cu(phen)₂](C1O₄)₃ (2) and dihydroxo-bridged copper(II) complexes [Cu₂(μ–OH)₂(bipy)₂]SO₄?·?5H₂O (3) and [Cu₂(μ–OH)₂(phen)₂]SO₄?·?5H₂O (4) (where bpy and phen are 2,2′-bipyridine and 1,10-phenanthroline, respectively) using the dispersive EXAFS beamline at 2?GeV Indus-2 synchrotron source at RRCAT, Indore, India. The EXAFS data have been analyzed using the software, Athena and Artemis. Theoretical models have been generated for 1 and 3 using available crystallographic data and then fitted to their experimental EXAFS data to obtain the structural parameters, which include bond-lengths, coordination numbers, and thermal disorders. The results obtained have been found to be comparable with their crystallographic results. As the crystallographic data for 2 and 4 are not available in the literature, we have determined their structural parameters by fitting their experimental EXAFS data with the same theoretical models which were generated for their corresponding analogous complexes 1 and 3, respectively. The structural parameters thus determined have been reported. Also, on the basis of the analysis of the EXAFS data, these four complexes have been shown to be binuclear, i.e. they contain two metals. Further, the values of the chemical shifts suggest that copper is in +2 oxidation state in these complexes.     

On the structure and spin states of Fe(III)-EDDHA complexes

DFT methods are suitable for predicting both the geometries and spin states of EDDHA-Fe(III) complexes. Thus, extensive DFT computational studies have shown that the racemic-Fe(III) EDDHA complex is more stable than the meso isomer, regardless of the spin state of the central iron atom. A comparison of the energy values obtained for the complexes under study has also shown that high-spin (S = 5/2) complexes are more stable than low-spin (S = 1/2) ones. These computational results matched the experimental results of the magnetic susceptibility values of both isomers. In both cases, their behavior has been fitted as being due to isolated high-spin Fe(III) in a distorted octahedral environment. The study of the correlation diagram also confirms the high-spin iron in complex 2b. The geometry optimization of these complexes performed with the standard 3-21G* basis set for hydrogen, carbon, oxygen, and nitrogen and the Hay-Wadt small-core effective core potential (ECP) including a double-xi valence basis set for iron, followed by single-point energy refinement with the 6-31G* basis set, is suitable for predicting both the geometries and the spin-states of EDDHA-Fe(III) complexes. The presence of a high-spin iron in Fe(III)-EDDHA complexes could be the key to understanding their lack of reactivity in electron-transfer processes, either chemically or electrochemically induced, and their resistance to photodegradation.     

Binuclear Pd(II) complexes with alkynyl ligands and functionalised tail-groups: Molecular and electronic structure studied by XPS and EXAFS

The binuclear transition metal dialkynyl bridged Pd(II) complexes trans,trans-[ClPd(PBu₃)₂–CC–C₆H₄–C₆H₄–CC–Pd(PBu₃)₂Cl] and trans,trans-[CH₃OC–S–Pd(PBu₃)₂–CC–C₆H₄–C₆H₄–CC–Pd(PBu₃)₂–S–COCH₃] were synthesized and investigated by X-ray Photoemission (XPS) and X-ray Absorption (XAS) spectroscopies. XPS measurements lead to assess that the thiolate terminal group does not affect dramatically the electronic structure of the transition metal, and as a consequence the two complexes are expected to possess analogous molecular structure. XAS data analysis suggested a square-planar geometry around the palladium center in both binuclear compounds.     

Simulating picosecond iron K-edge X-ray absorption spectra by ab initio methods to study photoinduced changes in the electronic structure of Fe(II) spin crossover complexes

Recent time-resolved X-ray absorption experiments probing the low-spin to high-spin photoconversion in Fe(II) complexes have monitored the complex interplay between electronic and structural degrees of freedom on an ultrafast time scale. In this study, we use transition potential (TP) and time-dependent (TD) DFT to simulate the picosecond time-resolved iron K-edge X-ray absorption spectrum of the spin crossover (SCO) complex, [Fe(tren(py)(3))](2+). This is achieved by simulating the X-ray absorption spectrum of [Fe(tren(py)(3))](2+) in its low-spin (LS), (1)A(1), ground state and its high-spin (HS), (5)T(2), excited state. These results are compared with the X-ray absorption spectrum of the high-spin analogue (HSA), [Fe(tren(6-Me-py)(3))](2+), which has a (5)T(2) ground state. We show that the TP-DFT methodology can simulate a 40 eV range of the iron K-edge XANES spectrum reproducing all of the major features observed in the static and transient spectra of the LS, HS, and HSA complexes. The pre-edge region of the K-edge spectrum, simulated by TD-DFT, is shown to be highly sensitive to metal-ligand bonding. Changes in the intensity of the pre-edge region are shown to be sensitive to both symmetry and π-backbonding by analysis of relative electric dipole and quadrupole contributions to the transition moments. We generate a spectroscopic map of the iron 3d orbitals from our TD-DFT results and determine ligand field splitting energies of 1.55 and 1.35 eV for the HS and HSA complexes, respectively. We investigate the use of different functionals finding that hybrid functionals (such as PBE0) produce the best results. Finally, we provide a detailed comparison of our results with theoretical methods that have been previously used to interpret Fe K-edge spectroscopy of equilibrium and time-resolved SCO complexes.     

Dinuclear Fe(III) complexes with spin crossover

Abstract  A series of dinuclear Fe(III) complexes was synthesized in which the Schiff-base blocking ligand L⁵ coordinates each of the centers which are linked by a bidentate, bipyridine-type ligand. For these systems, [L⁵Fe^III{bridge}Fe^IIIL⁵](BPh₄)₂, thermally induced spin crossover is observed. The corollary of the systems is that the spin crossover interferes with the magnetic exchange interaction. The overlap of the energy bands of the LL and HH reference states (L, low-spin; H, high-spin) causes the exchange interaction to act against the spin crossover (leading to incompleteness or gradual behavior). Graphical abstract        

Synthesis with structural and electronic characterization of homoleptic Fe(II)- and Fe(III)-fluorinated phenolate complexes

Four Fe(III) compounds and one Fe(II) compound containing mononuclear, homoleptic, fluorinated phenolate anions of the form [Fe(OAr)(m)](n-) have been prepared in which Ar(F) = C(6)F(5) and Ar' = 3,5-C(6)(CF(3))(2)H(3): (Ph(4)P)(2)[Fe(OAr(F))(5)], 1, (Me(4)N)(2)[Fe(OAr(F))(5)], 2, {K(18-crown-6)}(2)[Fe(OAr(F))(5)], 3a, {K(18-crown-6)}(2)[Fe(OAr')(5)], 3b, and {K(18-crown-6)}(2)[Fe(OAr(F))(4)], 6. Two dinuclear Fe(III) compounds have also been prepared: {K(18-crown-6)}(2)[(OAr(F))(3)Fe(μ(2)-O)Fe(OAr(F))(3)], 4, and {K(18-crown-6)}(2)[(OAr(F))(3)Fe(μ(2)-OAr(F))(2)Fe(OAr(F))(3)], 5. These compounds have been characterized with UV-vis spectroscopy, elemental analysis, Evans method susceptibility, and X-ray crystallography. All-electron, geometry-optimized DFT calculations on four [Ti(IV)(OAr)(4)] and four [Fe(III)(OAr)(4)](-) species (Ar = 2,3,5,6-C(6)Me(4)H, C(6)H(5), 2,4,6-C(6)Cl(3)H(2), C(6)F(5)) with GGA-BP and hybrid B3LYP basis sets demonstrated that, under D(2d) symmetry, π donation from the O 2p orbitals is primarily into the d(xy) and d(z(2)) orbitals. The degree of donation is qualitatively consistent with expectations based on ligand Br?nsted basicity and supports the contention that fluorinated phenolate ligands facilitate isolation of nonbridged homoleptic complexes due to their reduced π basicity at oxygen.     

Simplified formula for the1 A 1⇄5 T 2 spin transition temperature in Fe(II) complexes

A formula relating the¹A₁?⁵T₂ spin transition temperature (T_c) in Fe(II) complexes to characteristics of the compounds is derived. With certain assumptions, T_c is determined by the splitting parameter Δ_LS of e_g- and t_2g-orbitals for the low-spin complexes and by the frequency ratio of normal vibrations of the low- and high-spin phases. For the group of compounds possessing spin transitions, the values of Δ_LS are found and analyzed. Correlations between T_c and Δ_LS are established; the values of the change in the probability of the Mössbauer effect are correlated with those of entropy of spin transition. The correlations are substantiated. It is concluded that for mononuclear Fe(II) complexes possessing sharp spin transitions, T_c may not be significantly higher than for Fe(Phy)₂(BF₄)₂ (T_c=282 K).     

An SCF XαSW study of the electronic structure and X-ray and photoelectron spectra of Fe(II) and Fe(III) hexacyano complexes in a cluster approach

The electronic structure of the hexacyano complexes [Fe(CN)₆]^4– and [Fe(CN)₆]^3– as clusters of the cyanide complex salts has been calculated by the SCF XSW method. Theoretical photoelectron, X-ray emission and absorption spectra have been constructed. The contribution of the resonance emission to the X-ray emission spectra has been estimated. On the basis of detailed comparison of the theoretical and experimental spectra an assignment of the fine structure of the spectra has been proposed.     

Cu(I) and Fe(II) complexes with N,N-dimethylthioformamide and Fe(II) complexes with N,N-dimethylformamide

The synthesis of the following Cu(I) and Fe(II) complexes with N,N-dimethylthioformamide (DMTF) and N,N-dimethylformamide (DMF) are described: Cu(DMTF)₄ClO₄, Cu(DMTF)₂Cl, Cu(DMTF)₂Br, Cu(DMTF)₂I, Fe(DMTF)₆(ClO₄)₂, Fe(DMTF)₂Cl₂, Fe(DMTF)₂Br₂, Fe(DMTF)₂I₂, Fe(DMF)₆(ClO₄)₂, Fe(DMF)₂Cl₂, Fe(DMF)Br₂ and Fe(DMF)₃I₂. Electronic absorption spectra, IR spectra, magnetic susceptibilities of the solids and in solution as well as conductivities have been measured of these compounds in order to obtain information on the nature of the interaction between the cations and the ligands, the coordination in the crystalline state, in solution and the dissociation of these compounds in the respective solvents.     

Comparative study on the photophysical properties between carbene-based Fe (II) and Ru (II) complexes

The comparative study on the photophysical properties between cheap metal Fe (II) complexes and noble metal Ru (II) complexes with identical ligand coordination is performed by the combination of density functional theory (DFT) and time-dependent density functional theory (TDDFT) to evaluate the potential alternative applications of Fe (II) complexes. RuBIP (BIP = 2,6-bis (imidazol-2- ylidene)pyridine) is theoretically established that the radiative lifetime of the second lowest triplet state is more consistence with experimental value. However, FeBIP retains nonluminous because of low-lying ³MC originated from weak d orbital splitting. FeBIPC (FeBIP with carboxylic acid groups) has twice longer lifetime than its parent complex FeBIP due to the great decrease of the energy gap between ³MLCT and ³MC. What's more, the lifetimes of Fe (II) complexes detected in the experiments are more accessible to nonradiative decay lifetimes of ³MC. The carboxylic acid groups are beneficial for the improvement of luminescent possibility and controllability of Fe (II) complexes, while there is still a huge challenge for effective material replacement comparing with Ru (II) complexes.     

QTAIM study of transition metal complexes with cyclophosphazene-based multisite ligands II. Cobalt(II) complexes

[(CoLCl)CoCl₃], [(CoMeLCl)CoCl₃], [(CoLBr)CoBr₃], [CoLBr]⁺ and [CoMeLBr₂] complexes, L = hexakis(2-pyridyloxy)cyclotriphosphazene, MeL = hexakis(4-methyl-2-pyridyloxy)cyclotriphosphazene, in the most stable high spin states are investigated at DFT level of theory using hybrid B3LYP functional. The exchange coupling parameter evaluated using a broken symmetry treatment increases with the ligands mass. Electron density is evaluated in terms of QTAIM (Quantum Theory of Atoms-in-Molecule) topological analysis of electron density. The bonds of central Co atoms with phosphazene nitrogens are shorter, stronger and more polar than with the aromatic pyridine nitrogens and their higher ellipticities may be explained by the π contribution from the phosphazene ring. The atomic charges of phosphazene nitrogens are ca. twice more negative than at the pyridine ones.     

High-pressure magnetic susceptibility studies of spin-state transition in Fe(II) complexes

High-pressure magnetic susceptibility measurements have been carried out on Fe(dipy)₂(NCS)₂ and Fe(phen)₂(NCS)₂ in the pressure range 1–10 kbar and tempeature range 80–300 K in order to investigate the factors responsible for the spin-state transitions. The transitions change from first order to second or higher order upon application of pressure. The temperature variation of the susceptibility at different pressures has been analysed quantitatively within the framework of available models. It is shown that the relative magnitudes of the ΔG⁰ of high-spin and low-spin conversion and the ferromagnetic interaction between high-spin complexes determines the nature of the transition.     

QTAIM study of transition metal complexes with cyclophosphazene-based multisite ligands I: Zinc(II) and nickel(II) complexes

The metal–ligand bonds in [(ZnCl₂)₂L], [NiLCl]⁺ and two isomers of [NiLCl₂] complexes with multimodal ligand L = hexakis(2-pyridyloxy)cyclotriphosphazene, cyclo-[NP(NC₅H₄O)₂]₃, are investigated at DFT level of theory using hybrid B3LYP functional. Electron density is evaluated in terms of QTAIM (quantum theory of atoms-in-molecule) topological analysis of electron density. The bonds of central transition metal atoms with phosphazene nitrogens are shorter, stronger and more polar than with the aromatic pyridine nitrogens. The atomic charges of phosphazene nitrogens are ca twice more negative than at the pyridine ones. The higher mechanical strain in the five-coordinate metal complexes than in the six-coordinate ones may be concluded.