A new family of nonanuclear lanthanide clusters displaying magnetic and optical properties

The initial employment of 2-(hydroxymethyl)pyridine in 4f metal chemistry has afforded a new family of Ln(III)(9) clusters with a sandglass-like topology and dual physical properties; the Dy(III) member shows single-molecule magnetism behavior, while the Eu(III) analogue exhibits intense red photoluminescence.     

Renormalized perturbation theory flow equations for the Anderson impurity model

We apply the renormalized perturbation theory (RPT) to the symmetric Anderson impurity model. Within the RPT framework exact results for physical observables such as the spin and charge susceptibility can be obtained in terms of the renormalized values \(\tilde \mu = (\tilde \Delta ,\tilde U)\) of the hybridization Δ and Coulomb interaction U of the model. The main difficulty in the RPT approach usually lies in the calculation of the renormalized values themselves. In the present work we show how this can be accomplished by deriving differential flow equations describing the evolution of \(\tilde \mu = (\tilde \Delta )\) with Δ. By exploiting the fact that \(\tilde \mu = (\tilde \Delta )\) can be determined analytically in the limit Δ → ∞ we solve the flow equations numerically to obtain estimates for the renormalized parameters in the range 0 <U/πΔ< 3.5.     

Di-2-pyridyl ketone/benzoate/azide combination as a source of copper(II) clusters and coordination polymers: dependence of the product identity on the solvent

The reactions of di-2-pyridyl ketone with Cu(O2CPh)2 in the presence of NaN3 and LiOH have led to an antiferromagnetically coupled (S = 0) Cu(II)6 cluster with a novel core and to (Cu(II)8)n and (Cu(II)2)n coordination polymers (the former 1D and the latter 2D) with interesting structures. The cluster or polymer formation depends on the reaction solvent.     

Structural motifs of diiodine complexes with amides and thioamides

The reaction of 2-pyrimidone hydrochloride ([C(4)H(5)N(2)O](+)[Cl](-) or [PMOH(2)](+)[Cl](-)) with diiodine in a dichloromethane-methanol solution resulted in the formation of ([C(4)H(5)N(2)O](+))(2)[I(2)Cl(2)](2-) (1) complex. The compound was characterized by elemental analysis, FT-IR, DTA-TG and conductivity titrations. The crystal structure of 1 was also determined by X-ray diffraction at 294(1) K. Compound 1 is monoclinic, space group P2(1)/n, consisting of two cationic [PMOH(2)](+) species and a [I(2)Cl(2)](2-) counter dianion. The cation is in its keto form. Direct reaction of thiazolidine-2-thione (tzdtH), with diiodine in dichloromethane solution, on the other hand, led to the formation of a crystalline solid which contained two complexes of formulae [(tzdtH)(2)I](+)[I(3)](-).2I(2) (2) and [(tzdtH)I(2)](2).I(2) (2a) in a ratio of 90 to 10%. Complex 2a was characterized by X-ray analysis at 180(2) K. Compound is monoclinic, space group C2/c and contains two units of [(tzdtH)I(2)] "spoke" structures. Compound 1, as well as the known species iodonium salt [(tzdtH)(2)I](+)[I(3)](-).2I(2) (2) and the charge transfer (CT) iodine complexes of formulae [(bztzdtH)I(2)] (3) and [(bztzdtH)I(2)].I(2) (4) (bztzdtH = 2-mercaptobenzothiazole) with "spoke" and extended "spoke" structures respectively, were tested for their oxidizing activity towards 3,5-di-tert-butylcatechol to 3,5-di-tert-butyl-o-benzoquinone.     

The Efficiency of RP-TLC for Lipophilicity Assessment. A Comparative Study on a Series of Pyrrolyl-Acetic Acid Derivatives,Inhibitors of Aldose Reductase

JPC – Journal of Planar Chromatography – Modern TLC - The lipophilicity of a series of pyrrolyl-acetic acid derivatives, inhibitors of the aldose reductase enzyme, was assessed by...     

Investigating magnetostructural correlations in the pseudooctahedral trans-[Ni(II){(OPPh2)(EPPh2)N}2(sol)2] complexes (E = S, Se; sol = DMF, THF) by magnetometry, HFEPR, and ab initio quantum chemistry

In this work, magnetometry and high-frequency and -field electron paramagnetic resonance spectroscopy (HFEPR) have been employed in order to determine the spin Hamiltonian (SH) parameters of the non-Kramers, S = 1, pseudooctahedral trans-[Ni(II){(OPPh(2))(EPPh(2))N}(2)(sol)(2)] (E = S, Se; sol = DMF, THF) complexes. X-ray crystallographic studies on these compounds revealed a highly anisotropic NiO(4)E(2) coordination environment, as well as subtle structural differences, owing to the nature of the Ni(II)-coordinated solvent molecule or ligand E atoms. The effects of these structural characteristics on the magnetic properties of the complexes were investigated. The accurately HFEPR-determined SH zero-field-splitting (zfs) D and E parameters, along with the structural data, provided the basis for a systematic density functional theory (DFT) and multiconfigurational ab initio computational analysis, aimed at further elucidating the electronic structure of the complexes. DFT methods yielded only qualitatively useful data. However, already entry level ab initio methods yielded good results for the investigated magnetic properties, provided that the property calculations are taken beyond a second-order treatment of the spin-orbit coupling (SOC) interaction. This was achieved by quasi-degenerate perturbation theory, in conjunction with state-averaged complete active space self-consistent-field calculations. The accuracy in the calculated D parameters improves upon recovering dynamic correlation with multiconfigurational ab initio methods, such as the second-order N-electron valence perturbation theory NEVPT2, the difference dedicated configuration interaction, and the spectroscopy-oriented configuration interaction. The calculations showed that the magnitude of D (～3-7 cm(-1)) in these complexes is mainly dominated by multiple SOC contributions, the origin of which was analyzed in detail. In addition, the observed largely rhombic regime (E/D = 0.16-0.33) is attributed to the highly distorted metal coordination sphere. Of special importance is the insight by this work on the zfs effects of Se coordination to Ni(II). Overall, a combined experimental and theoretical methodology is provided, as a means to probe the electronic structure of octahedral Ni(II) complexes.     

Hexanuclear iron(III) salicylaldoximato complexes presenting the [Fe6(mu3-O)2(mu2-OR)2]12+ core: syntheses, crystal structures, and spectroscopic and magnetic characterization

The use of salicylaldehyde oxime (H2salox) in iron(III) carboxylate chemistry has yielded two new hexanuclear compounds [Fe6(mu3-O)2(O2CPh)10(salox)2(L)2].xMeCN.yH2O [L = MeCONH2, x = 6, y = 0 (1); L = H2O, x = 2, y = 3 (2)]. Compound 1 crystallizes in the triclinic space group P with (at 25 degrees C) a = 13.210(8) A, b = 13.87(1) A, c = 17.04(1) A, alpha = 105.79(2) degrees , beta = 96.72(2) degrees , gamma = 116.69(2) degrees , V = 2578.17(2) A(3), and Z = 1. Compound 2 crystallizes in the monoclinic space group C2/c with (at 25 degrees C) a = 21.81(1) A, b = 17.93(1) A, c = 27.72(1) A, beta = 111.70(2) degrees , V = 10070(10) A(3), and Z = 4. Complexes 1 and 2 contain the [Fe6(mu3-O)2(mu2-OR)2]12+ core and can be considered as two [Fe3(mu3-O)] triangular subunits linked by two mu2-oximato O atoms of the salox2- ligands, which show the less common mu3:eta1:eta2:eta1 coordination mode. The benzoato ligands are coordinated through the usual syn,syn-mu2:eta1:eta1 mode. The terminal MeCONH2 ligand in 1 is the hydrolysis product of the acetonitrile solvent in the presence of the metal ions. M?ssbauer spectra from powdered samples of 2 give rise to two well-resolved doublets with an average isomer shift consistent with that of high-spin Fe(III) ions. The two doublets, at an approximate 1:2 ratio, are characterized by different quadrupole splittings and are assigned to the nonequivalent Fe(III) ions of the cluster. Magnetic measurements of 2 in the 2-300 K temperature range reveal antiferromagnetic interactions between the Fe(III) ions, stabilizing an S = 0 ground state. NMR relaxation data have been used to investigate the energy separation between the low-lying states, and the results are in agreement with the susceptibility data.     

Preparation and characterization of Ni(dpedt)(pddt) and Ni(dpedt)(pddt)·CS2, where dpedt is diphenylethylenedithiolate and pddt is 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate

The unsymmetrical nickel 1,2-dithiolene complex based on diphenylethylenedithiolate (dpedt) and 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate (pddt) was prepared and characterized. Depending on the conditions of crystallization, it is possible to obtain the complex in two different crystalline forms. X-ray structure studies recognize these forms as Ni(dpedt)(pddt) and Ni(dpedt)(pddt)·CS₂. The experimental optical and electrochemical parameters are in a good agreement with the calculated ones, using the corresponding parameters of the symmetrical complexes, Ni(dpedt)₂ and Ni(pddt)₂. The HOMO and LUMO energy levels, obtained from optical and electrochemical measurements, are very close to the Fermi energy of (metallic) Au. The chemical and electrochemical properties of both forms showed that they are stable in air and could be candidate materials for optics and electronics.     

Enhanced algebraic substructuring for symmetric generalized eigenvalue problems

This article proposes a new substructuring algorithm to approximate the algebraically smallest eigenvalues and corresponding eigenvectors of a symmetric positive-definite matrix pencil $(A,M)$. The proposed approach partitions the graph associated with $(A,M)$ into a number of algebraic substructures and builds a Rayleigh–Ritz projection subspace by combining spectral information associated with the interior and interface variables of the algebraic domain. The subspace associated with interior variables is built by computing substructural eigenvectors and truncated Neumann series expansions of resolvent matrices. The subspace associated with interface variables is built by computing eigenvectors and associated leading derivatives of linearized spectral Schur complements. The proposed algorithm can take advantage of multilevel partitionings when the size of the pencil. Experiments performed on problems stemming from discretizations of model problems showcase the efficiency of the proposed algorithm and verify that adding eigenvector derivatives can enhance the overall accuracy of the approximate eigenpairs, especially those associated with eigenvalues located near the origin.