nlstac: Non-Gradient Separable Nonlinear Least Squares Fitting

A new package for nonlinear least squares fitting is introduced in this paper. This package implements a recently developed algorithm that, for certain types of nonlinear curve fitting, reduces the number of nonlinear parameters to be fitted. One notable feature of this method is the absence of initialization which is typically necessary for nonlinear fitting gradient-based algorithms. Instead, just some bounds for the nonlinear parameters are required. Even though convergence for this method is guaranteed for exponential decay using the max-norm, the algorithm exhibits remarkable robustness, and its use has been extended to a wide range of functions using the Euclidean norm. Furthermore, this data-fitting package can also serve as a valuable resource for providing accurate initial parameters to other algorithms that rely on them

Structure, DFT Calculations, and Magnetic Characterization of Coordination Polymers of Bridged Dicyanamido-Metal(II) Complexes

Three coordination polymers of metal(II)-dicyanamido (dca) complexes with 4-methoxypyridine-N-oxide (4-MOP-NO); namely, catena-[Co(µ1,5-dca)2(4-MOP-NO)2] (1), catena-[Mn(µ1,5-dca)2(4-MOP-NO)2] (2), catena-[Cd(µ1,5-dca)2(4-MOP-NO)2] (3), and the mononuclear [Cu(κ1dca)2(4-MOP-NO)2] (4), were synthesized in this research. The complexes were analyzed by single crystal X-ray diffraction as well as spectroscopic methods (UV/vis, IR). The polymeric 1-D chains in complexes 1-3 were achieved by the doubly µ1,5-bridging dca ligands and the O-donor atoms of two axial 4-MOP-NO molecules in trans configuration around the distorted M(II) octahedral. On the other hand, the two "trans-axial" pyridine-N-oxide molecules in complexes 2 and 3 display opposite orientation (s-trans). The DFT (density functional theory) computational studies on the complexes 1-3 were consistent with the experimentally observed crystal structures. Compounds 1 and 2 display weak antiferromagnetic coupling between metal ions (J = −10.8 for 1 and −0.35 for 2)

Diverse coordination numbers and geometries in pyridyl adducts of lanthanide(III) complexes based on beta-diketonate

t: Ten mononuclear rare earth complexes of formula [La(btfa)3 (H2O)2 ] (1), [La(btfa)3 (4,40 - Mt2bipy)] (2), [La(btfa)3 (4,40 -Me2bipy)2 ] (3), [La(btfa)3 (5,50 -Me2bipy)2 ] (4), [La(btfa)3 (terpy)] (5), [La(btfa)3 (phen)(EtOH)] (6), [La(btfa)3 (4,40 -Me2bipy)(EtOH)] (7), [La(btfa)3 (2-benzpy)(MeOH)] (8), [Tb(btfa)3 (4,40 -Me2bipy)] (9) and (Hpy)[Eu(btfa)4 ] (10), where btfa = 4,4,4-trifuoro-1-phenylbutane1,3-dionato anion, 4,40 -Mt2bipy = 4,40 -dimethoxy-2,20 -bipyridine, 4,40 -Me2bipy = 4,40 -dimethyl2,20 -bipyridine, 5,50 -Me2bipy = 5,50 -dimethyl-2,20 -bipyridine, terpy = 2,20 :60 ,20 -terpyridine, phen = 1,10-phenathroline, 2-benzpy = 2-(2-pyridyl)benzimidazole, Hpy = pyridiniumH+ cation) have been synthesized and structurally characterized. The complexes display coordination numbers (CN) eight for 1, 2, 9, 10, nine for 5, 6, 7, 8 and ten for 3 and 4. The solid-state luminescence spectra of Tb-9 and Eu-10 complexes showed the same characteristic bands predicted from the Tb(III) and Eu(III) ions. The Overall Quantum Yield measured (φTOT) at the excitation wavelength of 371 nm for both compounds yielded 1.04% for 9 and up to 34.56% for 10 years

1,8-Bis(silylamido)naphthalene complexes of magnesium and zinc synthesized through alkane elimination reactions

The reactions between magnesium or zinc alkyls and 1,8-bis(triorganosilyl)diaminonaphthalenes afford the 1,8-bis(triorganosilyl)diamidonaphthalene complexes with elimination of alkanes. The reaction between 1,8-C10H6(NSiMePh2H)2 and one or two equivalents of MgnBu2 affords two complexes with differing coordination environments for the magnesium; the reaction between 1,8-C10H6(NSiMePh2H)2 and MgnBu2 in a 1:1 ratio affords 1,8-C10H6(NSiMePh2)2{Mg(THF)2} (1), which features a single magnesium centre bridging both ligand nitrogen donors, whilst treatment of 1,8-C10H6(NSiR3H)2 (R3 = MePh2, iPr3) with two equivalents of MgnBu2 affords the bimetallic complexes 1,8-C10H6(NSiR3)2{nBuMg(THF)}2 (R3 = MePh2 2, R3 = iPr3 3), which feature four-membered Mg2N2 rings. Similarly, 1,8-C10H6(NSiiPr3)2{MeMg(THF)}2 (4) and 1,8-C10H6(NSiMePh2)2{ZnMe}2 (5) are formed through reactions with the proligands and two equivalents of MMe2 (M = Mg, Zn). The reaction between 1,8-C10H6(NSiMePh2H)2 and two equivalents of MeMgX affords the bimetallic complexes 1,8-C10H6(NSiMePh2)2(XMgOEt2)2 (X = Br 6; X = I 7). Very small amounts of [1,8-C10H6(NSiMePh2)2{IMg(OEt2)}]2 (8), formed through the coupling of two diamidonaphthalene ligands at the 4-position with concomitant dearomatisation of one of the naphthyl arene rings, were also isolated from a solution of 7

COVID-19 outbreaks in a transmission control scenario: challenges posed by social and leisure activities, and for workers in vulnerable conditions, Spain, early summer 2020

Severe acute respiratory syndrome coronavirus 2 community-wide transmission declined in Spain by early May 2020, being replaced by outbreaks and sporadic cases. From mid-June to 2 August, excluding single household outbreaks, 673 outbreaks were notified nationally, 551 active (>6,200 cases) at the time. More than half of these outbreaks and cases coincided with: (i) social (family/friends’ gatherings or leisure venues) and (ii) occupational (mainly involving workers in vulnerable conditions) settings. Control measures were accordingly applied

Bismuth sulphide-polymer nanocomposites from a highly soluble bismuth xanthate precursor

Bismuth sulphide nanocrystal-polymer hybrid layers are of interest for various optoelectronic, thermoelectric or sensing applications. In this work, we present a ligand-free in situ route for the formation of Bi2S 3 nanorods directly within a polymer matrix. For this purpose, we introduce a novel bismuth xanthate (bismuth(iii) O-3,3-dimethylbutan-2-yl dithiocarbonate), which is highly soluble in non-polar organic solvents. The analysis of the crystal structure revealed that the prepared bismuth xanthate crystallises in the monoclinic space group C2/c and forms dimers. The bismuth xanthate can be converted into nanocrystalline Bi2S3 with an orthorhombic crystal structure via a thermally induced solid state reaction at moderate temperatures below 200°C. In combination with the high solubility in non-polar solvents this synthetic route for Bi2S 3 is of particular interest for the preparation of Bi 2S3-polymer nanocomposites as exemplarily investigated on Bi2S3-poly(methyl methacrylate) and Bi2S 3-poly(3-hexylthiophene-2,5-diyl) (P3HT) nanocomposite layers. Atomic force and transmission electron microscopy revealed that Bi2S 3 nanorods are dispersed in the polymer matrix. Photoluminescence experiments showed a quenching of the P3HT fluorescence with increasing Bi 2S3 content in the hybrid layer. © 2013 The Royal Society of Chemistry

Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) n

Derivatisation of Grignard synthons "PhAeI(thf)(n)" (Ae = Mg-Ba) prepared in situ from reactions of metal filings and iodobenzene provides a one-pot synthesis of heteroleptic N donor alkaline earth iodide complexes. Protolysis of "PhAeI(thf)(n)" with 3,5-diphenylpyrazole (Ph(2)pzH) yields pyrazolate complexes [Mg-2(mu-Ph(2)pz)(2)(I)(2)(thf)(3)] (1), [Ae(Ph(2)pz)(I)(thf)(4)] (Ae = Ca (2), Sr (3)), and [Ba-2(Ph(2)pz)(2)(mu-I)(2)(thf)(8)] (4). Addition of the Ae-Ph moiety to carbodiimide MesN=C=NMes (Mes = 2,4,6-(CH3)(3)C6H2) gave a series of benzamidinate iodide complexes [Ca-2{(MesN)(2)CPh}(2)(mu-I)(2)(thf)(4)] (6), [Sr{(MesN)(2)CPh}(I)(thf)(4)] (7), and [{Ba{(MesN)(2)CPh}(mu-I)(thf)(3)}(infinity)] (8). By contrast a symmetrical magnesium complex [Mg{(MesN)(2)CPh}(2)(thf)] (5) was obtained by Schlenk redistribution. These syntheses proceed without pre-activation of the metal for strontium and barium, and after activation with 2 mol-% iodine for calcium. The heavy alkaline earth metal complexes are the first examples of heteroleptic halide pyrazolate or amidinate complexes for strontium and barium. Complexes 1, 3, 4 and 6-8 were characterised crystallographically, revealing diverse structural chemistry of heteroleptic amidinate and pyrazolate iodide complexes across the alkaline earth series. A highlight is [Ba{(MesN)(2)CPh}(mu-I)(thf)(3)](infinity) (8) - an iodide bridged infinite 1-D polymer

Five-Coordinated Geometries from Molecular Structures to Solutions in Copper(II) Complexes Generated from Polydentate-N-Donor Ligands and Pseudohalides

A novel series of mononuclear five-coordinated pseudohalido-Cu(II) complexes displaying distorted square bipyramidal: [Cu(L1)(NCS)2] (1), [Cu(L2)(NCS)2] (2) and [Cu(L3)(NCS)]ClO4 (5) as well as distorted trigonal bipyramidal: [Cu(isp3tren)(N3)]ClO4 (3), [Cu(isp3tren)(dca)]ClO4 (4) and [Cu(tedmpza)(dca)]ClO4·0.67H2O (6) geometries had been synthesized and structurally characterized using X-ray single crystal crystallography, elemental microanalysis, IR and UV-vis spectroscopy, and molar conductivity measurements. Different N-donor amine skeletons including tridentate: L1 = [(2-pyridyl)-2-ethyl)-(3,4-dimethoxy)-2-methylpyridyl]methylamine and L2 = [(2-pyridyl)-2-ethyl)-(3,5-dimethyl-4-methoxy)-2-methyl-pyridyl]methylamine, and tetradentate: L3 = bis(2-ethyl-di(3,5-dimethyl-1H-pyrazol-1-yl)-[2-(3,4-dimethoxy-pyridylmethyl)]amine, tedmpza = tris[(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]amine and isp3tren = tris[(2-isopropylamino)ethyl)]amine ligands were employed. Molecular structural parameters such as nature of coligand, its chelate ring size and steric environment incorporated into its skeleton, which lead to adopting one of the two limiting geometries in these complexes and other reported compounds are analyzed and correlated to their assigned geometries in solutions. Similar analysis were extended to other five-coordinated halido-Cu(II) complexes