Synthesis, characterization and structural analysis of complexes from 2,2':6',2''-terpyridine derivatives with transition metals.

The synthesis and structural characterization of three families of coordination complexes synthesized from 4'-phenyl-2,2':6',2''-terpyridine (8, Ph-TPY), 4'-(4-chlorophenyl)-2,2':6',2''-terpyridine (9, ClPh-TPY) and 4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine (10, MeOPh-TPY) ligands with the divalent metals Co2+, Fe2+, Mn2+ and Ni2+ are reported. The compounds were synthesized from a 1:2 mixture of the metal and ligand, resulting in a series of complexes with the general formula [M(R-TPY)2](ClO4)2 (where M = Co2+, Fe2+, Mn2+ and Ni2+, and R-TPY = Ph-TPY, ClPh-TPY and MeOPh-TPY). The general formula and structural and supramolecular features were determinated by single-crystal X-ray diffraction for bis(4'-phenyl-2,2':6',2''-terpyridine)nickel(II) bis(perchlorate), [Ni(C21H15N3)2](ClO4)2 or [Ni(Ph-TPY)2](ClO4)2, bis[4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine]manganese(II) bis(perchlorate), [Mn(C22H17N3O)2](ClO4)2 or [Mn(MeOPh-TPY)2](ClO4)2, and bis(4'-phenyl-2,2':6',2''-terpyridine)manganese(II) bis(perchlorate), [Mn(C21H15N3)2](ClO4)2 or [Mn(Ph-TPY)2](ClO4)2. In all three cases, the complexes present distorted octahedral coordination polyhedra and the crystal packing is determined mainly by weak C-H...π interactions. All the compounds (except for the Ni derivatives, for which FT-IR, UV-Vis and thermal analysis are reported) were fully characterized by spectroscopic (FT-IR, UV-Vis and NMR spectroscopy) and thermal (TGA-DSC, thermogravimetric analysis-differential scanning calorimetry) methods.

Fluorimetric determination of aqueous formaldehyde employing heating and ultrasound-assisted approach through its derivatization with a ß-diketone-nickel(2+) complex immobilized in a PMMA flow cell.

Formaldehyde (FA) is a highly toxic substance present in many matrices, including freshwater as well as found in natural mechanisms such as rainfall and combustion of organic matter. Consumption of water contaminated with high levels of FA can cause severe short-term or long-term health problems. Due to these health risks, procedures are necessary to determine and quantify FA in aqua sources This paper reports on a study of fluorimetric determination of FA using a nickel(2 + )-diketonate coordination compound immobilized as a solid precursor. The compound was characterized by electronic absorption, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetry (TG), optical microscopy (OM), and scanner electron microscopy (SEM). The methodology was based on the reaction of the synthesized compound with an ammoniacal buffer generating a selective reagent for formaldehyde: fluoral-P. The product of the reaction generates 3,5-diacetyl-1,4-dihydrolutidine (DDL), which is responsible for the fluorescence of the system. Several parameters such as temperature, duration of heating time, and dilution effect with the best effects were studied to carry out FA determination. Under the optimum experimental conditions, a linear response ranging from 1.0 to 10.0 mg/L FA (R = 0.997 and n = 10), and a detection (3σ criterion) and quantification (10 σ criterion) limit estimated at 0.129 and 0.389 mg/L, respectively were achieved. The FA analysis was able to be conducted in 05 min with a relative standard deviation estimated at 1.10 %.

Reactivity of NiII, PdII and PtII complexes bearing phosphine ligands towards ZnII displacement and hydrolysis in Cis2His2 and Cis3His zinc-fingers domains.

A systematic study of the effect of phosphine and bis-phosphine ligands in the interaction of NiII, PdII, and PtII complexes with two classes of zinc fingers was performed. The Cys2His2, finger 3 of specific protein-1, and the Cys2HisCys C-terminal zinc finger of nucleocapsid protein 7 of the HIV-1 were used as models of the respective class. In general, phosphine ligands favor the metal binding to the peptide, although the bis-phosphine ligands produce more specific binding than the monodentate. In the case of nickel complexes, the interaction of NiII ions with the sequence SKH, present in Cys2His2, results in hydrolysis, contrasting to the preferred zinc ejection produced by the NiII complexes with chelating phosphines, producing Ni(bis-phosphine) fingers. In the absence of the SKH sequence, zinc ejection is observed with the formation of nickel fingers, with reactivity dependent on the phosphine. On the other hand, Pd(phosphines) produces Pd2 fingers in the case of triphenylphosphine with the phosphine coordinated as intermediate species. The bis-phosphine ligands produce very clean spectra and a stable signal Pd(bis-phosphine)finger. Interestingly, phosphines produce very reactive platinum complexes, which eject zinc and promote peptide hydrolysis. The results reported here are relevant to the understanding of the mechanism of these interactions and how to modulate metallocompounds for zinc finger interference.

Enhanced Host-Guest Association and Fluorescence in Copolymers from Copper Salphen Complexes by Supramolecular Internalization of Anions.

We describe the synthesis, crystallographic characterization of a new Cu-Salphen compound and its use as a host Lewis-acid against guest anions in two versions: a) free molecule, b) copolymerized with methyl methacrylate:n-butyl acrylate (1 : 4-wt.) as protective co-monomers. Higher contents in Cu-Salphen yielded larger and more homogeneous polymer sizes. Polymer size together with glass transitions, heat capacity, thermal degradation, guest-saturation degrees and host-guest species distribution profiles from spectrophotometric titrations explained growths of up to 630-fold in K11 and 180000-fold in K12 for the host's binding site attributable to a solvophobic protection from the macromolecular structure. Spectrofluorimetry revealed blue-shifted×13-16 larger luminescence for Cu-Salphen in the polymers (λem =488-498 nm) than that of the non-polymerized counterpart (λem =510-543 nm) and "turn-on" blue-shifted enhanced fluorescence upon guest association. We propose a cooperative incorporation of the guests occurring from the outer medium toward internally protected binding site pockets in the random coil polymer conformations.

Syntheses, Characterization, and Antioxidant Evaluation of Cu2+, Mn2+, and Fe3+ Complexes with a 14 Membered EDTA-Derived Macrocycle.

The Cu2+, Mn2+, and Fe3+ complexes of a 14 membered macrocycle were synthesized and their antioxidant capacities were evaluated against ABTS and DPPH radicals, with the objective of collecting insights into the biomimetic role of the central metal ions. The macrocycle, abbreviated as H2L14, is a derivative of EDTA cyclized with 1,4-diamine, and the moderately flexible macrocyclic frame permits the formation of [ML14·H2O] chelates with octahedral coordination geometries common among the metal ions. The metal complexes were characterized by electrospray-ionization mass spectrometry, Fourier transform infrared spectroscopy, and Raman and X-ray photoelectron spectroscopic methods, as well as thermogravimetric analysis; the octahedral coordination geometries with water coordination were optimized by DFT calculations. The antioxidant assays showed that [FeL14·H2O]+ was able to scavenge synthetic radicals with moderate capacity, whereas the other metal chelates did not show significant activity. The Raman spectrum of DPPH in solution suggests that interaction was operative between the Fe3+ chelate and the radical so as to cause scavenging capability. The nature of the central metal ions is a controlling factor for antioxidant capacity, as every metal chelate carries the same coordination geometry.

Solution Studies and Crystal Structures of Heteropolynuclear Potassium/Copper Complexes with Phytate and Aromatic Polyamines: Self-Assembly through Coordinative and Supramolecular Interactions.

Phytate (L12- ) is a relevant natural product. It interacts strongly with biologically relevant cations, due to the high negative charge exhibited in a wide pH range. The synthesis and crystal structures of the mixed-ligand Cu(II) polynuclear complexes K(H2 tptz)0.5 [Cu(H8 L)(tptz)] ⋅ 3.6H2 O (1), K(H2 O)3 {[Cu(H2 O)(bpca)]3 (H8 L)} ⋅ 1.75H2 O (2), and K1.5 (H2 O)2 [Cu(bpca)](H9.5 L) ⋅ 8H2 O (3) (tptz=2,4,6-tri(pyridin-2-yl)-1,3,5-triazine; Hbpca=bis(2-pyridylcarbonyl) amine) are reported herein. They were obtained by the use of an aromatic rigid amine, which satisfies some of the metal coordination sites and promotes the hierarchical assembly of 2D polymeric structures. Speciation of phytate-Cu(II)-Hbpca system and determination of complex stability constants were performed by means of potentiometric titrations, in 0.15 M NMe4 Cl at 37.0 °C, showing that, even in solution, this system is able to produce highly aggregated complexes, such as [Cu3 (bpca)3 (H7 L)]2- . Furthermore, the Cu(II)-mediated tptz hydrolysis was studied by UV-vis spectroscopy at room temperature in 0.15 M NMe4 Cl. Based on the equilibrium results and with the aid of molecular modelling tools, a plausible self-assembly process for 2 and 3 could be proposed.

New complexes of Cu(II) with dipicolinate and pyridyl-based ligands: An experimental and DFT approach.

The three novel mononuclear copper(II) complexes with dipicolinate and pyridyl-based ligands [Cu(dipic)(L)(OH2)] (L=4-picoline, vinylpyridine, 4-styrylpyridine; dipic2-=dipicolinate) were afforded and structurally characterized. X-ray diffraction studies accounted for slight distorted square-pyramidal structures in which the dianion dipic2- acts as a tridentate ligand in a mer-fashion, the N-donor species occupy an in-plane position, and a water molecule was detected apically coordinated. To assess the effect of the nature of the pyridyl-substituent (para position) on electronic properties, other complexes were also synthesized: [Cu(dipic)(py)(OH2)], [{Cu(dipic)(OH2)}2(µ-pyz)] and [{Cu(dipic)(OH2)}(µ-pypy){Cu(dipic)}] (py=pyridine, pyz=pyrazine, pypy=(E)-1,2-bis(pyridine-4-yl)ethane). Absorptive behavior in the UV-VIS region was studied in solution and in the solid state (reflectance measurements). Additionally, geometry and population analyses were conducted by means of DFT calculations. Electronic UV-VIS spectra were simulated for both dinuclear complexes in the framework of the TD-DFT methodology to assign the origin of the absorption bands.