Dimensionality Control in Crystalline Zinc(II) and Silver(I) Complexes with Ditopic Benzothiadiazole-Dipyridine Ligands

Three 2,1,3-benzothiadiazole-based ligands decorated with two pyridyl groups, 4,7-di(2-pyridyl)-2,1,3-benzothiadiazol (2-PyBTD), 4,7-di(3-pyridyl)-2,1,3-benzothiadiazol (3-PyBTD) and 4,7-di(4-pyridyl)-2,1,3 benzothiadiazol (4-PyBTD), generate ZnII and AgI complexes with a rich structural variety: [Zn(hfac)2(2-PyBTD)] 1, [Zn2(hfac)4(2-PyBTD)] 2, [Ag(CF3SO3)(2-PyBTD)]23, [Ag(2-PyBTD)]2(SbF6)24, [Ag2(NO3)2(2-PyBTD)(CH3CN)] 5, [Zn(hfac)2(3-PyBTD)] 6, [Zn(hfac)2(4-PyBTD)] 7, [ZnCl2(4-PyBTD)2] 8 and [ZnCl2(4-PyBTD)] 9 (hfac = hexafluoroacetylacetonato). The nature of the resulting complexes (discrete species or coordination polymers) is influenced by the relative position of the pyridyl nitrogen atoms, the nature of the starting metal precursors, as well as by the synthetic conditions. Compounds 1 and 8 are mononuclear and 2, 3 and 4 are binuclear species. Compounds 6, 7 and 9 are 1D coordination polymers, while compound 5 is a 2D coordination polymer, the metal ions being bridged by 2-PyBTD and nitrato ligands. The solid-state architectures are sustained by intermolecular π–π stacking interactions established between the pyridyl group and the benzene ring from the benzothiadiazol moiety. Compounds 1, 2, 7–9 show luminescence in the visible range. Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TD-DFT) calculations have been performed on the ZnII complexes 1 and 2 in order to disclose the nature of the electronic transitions and to have an insight on the modulation of the photophysical properties upon complexation.

Competitive Adsorption of As(III), As(V), and PO4 by an Iron Oxide Impregnated Activated Carbon: Surface Complex Modeling

The objective of this study was to predict the competitive adsorption of As(III), As(V), and PO4 by an iron oxide impregnated carbon (L-Act, 9% Fe(III) amorphous iron oxide) over a range of environmental conditions using the surface complexation modeling (SCM) approach. L-Act surface complexation constants determined from a single pH-adsorption edge were used to predict pH-dependent competitive removal in singular, binary, and tertiary adsorbate systems. As(III), As(V), and PO4 complexes were modeled as bidentate binuclear species at low pH and monodentate species at high pH using the two monoprotic surface site/diffuse electric double layer model (2MDLM). F values determined based on 2MDLM predictions were close to those calculated by FITEQL (a statistical optimization program) demonstrating the effectiveness of the 2MDLM in describing adsorption behavior. F values were generally in the recommended range of 0.1–20 indicating a good fit between the data and the model. The 2MDLM also successfully predicted As(III)/As(V)/PO4 adsorption data of hydrous ferric oxide and goethite adsorbents from the literature.

Synthesis and Characterization of a Binuclear Copper(II)-dipyriamethyrin Complex: [Cu2(dipyriamethyrin)(μ2-1,1-acetato)2]

The reaction between dipyriamethyrin and copper(II) acetate [Cu(OAc)2] afforded what is, to our knowledge, the first transition metal-dipyriamethyrin complex. Molecular and electronic characterization of this binuclear Cu(II) complex via EPR, UV-vis, and single crystal X-ray diffraction analysis revealed marked differences between the present constructs and previously reported binuclear copper(II) hexaphyrin species. UV-vis titration analyses provided evidence for a homotropic positive allosteric effect, wherein the binuclear species is formed without significant intermediacy of a monomeric complex.

X-Ray Structural Studies of Small-Bite Ligands on Large Cations – Lanthanide(III) Ions and Dimethylphosphate

Reactions of lanthanide chlorides or trifluoracetates (tfa) or picrates with trimethylphosphate alone in the first two cases or trimethylphosphate plus 1,10-phenanthroline or 2,2′;6′,2′′-terpyridine in the third, result in the formation of crystalline products containing dimethylphosphate (dmp–). Single crystal X-ray structural characterisation of these materials has shown that the stoichiometrically simple Ln(dmp)3 species obtained with chloride reactants and the lighter lanthanides are polymeric and commonly dimorphic, while the stoichiometrically more variable mixed dmp/tfa complexes have structures closely related to one phase of the Ln(dmp)3 family, and the presence of picrate and aza-aromatic ligands enables the isolation of Y and Lu derivatives containing binuclear species. In all, the dmp– ligands adopt exclusively the κ1O;κ1O′ bridging mode, the overall results indicating that this should apply to the complete lanthanide series.

Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data

Poly(ethylene phosphates) are promising polymers for use in biomedical applications. Catalytic ring-opening polymerization (ROP) of cyclic ethylene phosphate monomers (CEPMs) is the most effective approach for obtaining these polymers. The mechanism of coordination ROP of CEPMs remains unclear. We report, for the first time, the results of DFT modeling of CEPM ROP. In these calculations by Gaussian-09 program package with the B3PW91/DGTZVP basis set, we explored methyl ethylene phosphate (MeOEP) ROP catalyzed by dimeric and monomeric catalytic species derived from heteroleptic complex [(BHT)Mg(μ-OBn)(THF)]2 (Mg1, BHT = 2,6-di-tert-butyl-4-methylphenolate). Analysis of the reaction profiles for the binuclear and mononuclear reaction mechanisms allowed us to conclude that the ROP of MeOEP is preferentially catalyzed by mononuclear Mg complexes. This estimation was confirmed by comparative polymerization experiments using MeOEP and traditional monomers ε-caprolactone (εCL), racemic lactide (rac-LA), and l-lactide (l-LA) initiated by Mg1. ROP of MeOEP proceeds at an extremely high rate due to the substantially lower activation barrier calculated for mononuclear mechanism in comparison with that of cyclic esters that polymerize without the dissociation of BHT-Mg binuclear species. We also demonstrated the use of MeOEP as a "monomerization" agent in the synthesis of MeOEP-lactide block copolymers. Comparison of the multiple acceleration of l-LA ROP after MeOEP prepolymerization and formation of atactic PLA blocks in rac-LA polymerization with the heterotactic PLA formation during Mg1-catalyzed homopolymerization also confirmed the mononuclear nature of the polyphosphate-containing catalytic particles.

EMISSÃO QUASE BRANCA DE UM COMPLEXO BINUCLEAR DE DISPRÓSIO(III) CONTENDO DICARBOXILATOS

This work reports the synthesis and characterization of the novel [Dy2(dcpz)2(suc)(H2O)8](H2O)1.5 (dcpz = 3,5-dicarboxypyrazolate, suc = succinate). The structure should probably consist of a binuclear species in which Dy3+ ions are linked by two different bridging organic ligands. Luminescent studies were carried out and revealed that the Dy3+complex exhibits a near white emission under UV excitation.

A comparative insight into the bioactivity of mono- and binuclear silver(I)-N-heterocyclic carbene complexes: synthesis, lipophilicity and substituent effect

Silver(I)-N-heterocyclic carbene (Ag(I)-NHC) complexes of mononuclear and binuclear species, synthesised by our group and others in recent years, offer a fascinating outlook on their bioactivity. These complexes advance a range of adaptable structural patterns, leading to intra-specific variation in anticancer and antimicrobial activities. This study therefore reviews the synthesis, structural analysis and bioactivity of Ag complexes derived from mononuclear-NHC complexes either with coordinating or non-coordinating anions and binuclear NHC complexes. Specifically, the effect of stability, chain lengths and lipophilicity on the biological activity of recently reported Ag(I)-NHC complexes is reviewed. These complexes can be further explored as novel antibacterial and anticancer drugs in the nearest future.

Crystal structure of bis[μ-S-hexyl 3-(2-oxidobenzylidene)dithiocarbazato-κ4O,N3,S:O]dicopper(II)

The title compound, [Cu2(C14H18N2OS2)2], is a binuclear copper(II) complex of an oxybenzylidenedithiocarbazate ligand. The ligand coordinates in a tridentate manner through N-, S- and O-donor atoms. Each O atom also bridges to a second CuIIion to form the binuclear species. It has a central Cu2O2rhomboid moiety and a metal-to-metal separation of 2.9923 (6) Å. In the crystal, the binuclear complexes stack along theaaxis with all the hexyl chains located side-by-side, forming a hydrophobic region. The complexes are linkedviaC—H...N hydrogen bonds, forming chains along thec-axis direction. One CuIIatom has the S atom of a symmetry-related complex located approximately in the apical position at 2.9740 (11) Å. This weak interaction links the chains to form slabs parallel to theacplane.

(μ-1,2-Dimethoxyethane-κ2O:O′)bis[(1,2-dimethoxyethane-κ2O,O′)tris(1,1,1,5,5,5-hexafluoro-4-oxopent-2-en-2-olato-κ2O,O′)cerium(III)]

A previous analysis [Fatilaet al.(2012).Dalton Trans.41, 1352–1362] of the title complex, [Ce2(C5HF6O2)6(C4H10O2)3], had identified it as Ce(hfac)3(dme)1.5according to the1H NMR integration [hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate (1,1,1,5,5,5-hexafluoro-4-oxopent-2-en-2-olate) and dme = 1,2-dimethoxyethane]; however, it was not possible to determine the coordination environment unambiguously. The structural data presented here reveal that the complex is a binuclear species located on a crystallographic inversion center. Each CeIIIion is coordinated to three hfac ligands, one bidentate dme ligand and one monodentate (bridging) dme ligand, thus giving a coordination number of nine (CN = 9) to each CeIIIion. The atoms of the bridging dme ligand are unequally disordered over two sets of sites. In addition, in two of the –CF3groups, the F atoms are rotationally disordered over two sets of sites. This is the first crystal structure of a binuclear lanthanide β-diketonate with a bridging dme ligand.