Synthesis, crystal structure, and spectroscopic and thermal properties of the polymeric compound catena-poly[[bis(2,4-dichlorobenzoato)zinc(II)]-µ-isonicotinamide].

Zinc(II) carboxylates with O-, S- and N-donor ligands are interesting for their structural features, as well as for their antibacterial and antifungal activities. The one-dimensional zinc(II) coordination complex catena-poly[[bis(2,4-dichlorobenzoato-κO)zinc(II)]-µ-isonicotinamide-κ(2)N(1):O], [Zn(C7H3Cl2O2)2(C6H6N2O)]n, has been prepared and characterized by IR spectroscopy, single-crystal X-ray analysis and thermal analysis. The tetrahedral ZnO3N coordination about the Zn(II) cation is built up by the N atom of the pyridine ring, an O atom of the carbonyl group of the isonicotinamide ligand and two O atoms of two dichlorobenzoate ligands. Isonicotinamide serves as a bridge between tetrahedra, with a Zn···Zn distance of 8.8161 (7) Å. Additionally, π-π interactions between the planar benzene rings contribute to the stabilization of the extended structure. The structure is also stabilized by intermolecular hydrogen bonds between the amino and carboxylate groups of the ligands, forming a two-dimensional network. During thermal decomposition of the complex, isonicotinamide, dichlorobenzene and carbon dioxide were evolved. The final solid product of the thermal decomposition heated up to 1173 K was metallic zinc.

Effect of fluorine position on the coordinating ability of fluorosalicylic acids--an experimental study complemented with computations.

The complexation of 3-, 4-, and 6-fluorosalicylic acids (HL) with copper(II) was investigated in aqueous solution by pH-potentiometry combined with UV-visible spectrophotometry, and in 50 v/v % water-methanol mixture by the two-dimensional ESR simulation method. Both methods showed the formation of [CuLH(-1)] and [CuL(2)H(-2)](2-) of high stabilities, and, at low excess of ligand, the ESR-silent mixed hydroxido complex [Cu(2)L(2)H(-3)](-). Further species were also identified by the two-dimensional ESR simulation method: [CuL](+) in the acidic region, the minor dimer [Cu(2)L(2)H(-2)], and the cis and the trans isomers for [CuL(2)H(-2)](2-). The position of the fluorine atom in the aromatic ring had significant effect on the coordination abilities of the ligands, in good correlation with their reported biological activities. It was 3-fluorosalicylic acid, which formed the most stable complexes [CuLH(-1)] and [CuL(2)H(-2)](2-), while the mononuclear complexes with 6-fluorosalicylic acid were found to be the least stable. For the other ligands (including 5-fluorosalicylic acid studied recently), complexes of medium stabilities were formed. For the interpretation of these findings, ab initio and semi-empirical quantum chemical calculations were carried out for the ligand molecules, isolated and surrounded by water molecules, respectively.

Equilibria of 3-pyridylmethanol with copper(II). A comparative electron spin resonance study by the decomposition of spectra in liquid and frozen solutions.

The copper(II)-3-pyridylmethanol (L) system was investigated in aqueous solution by two-dimensional ESR evaluation at 298 K, and computer simulation of the individual anisotropic spectra at 77 K. The data revealed that the paramagnetic copper(II) complexes [CuL] (2+), [CuL 2] (2+), [CuL 3] (2+), and [CuL 4] (2+) are formed up to pH approximately 7 at a moderate or high excess of ligand. As compared with chelating ligands, two differences were observed for the complexation of 3-pyridylmethanol with copper(II): (1) In contrast with the well-resolved spectra in frozen solution, considerable line-broadening and distortion of the spectral shapes were seen at 298 K, which was interpreted in terms of isomeric equilibria and the medium-rate interconversion of various complexes on the ESR time-scale. (2) At low temperature, there were dramatic changes in the concentration distribution, the minor complexes with higher numbers of coordinating ligands ([CuL 3] (2+) and in particular [CuL 4] (2+)) becoming strongly favored. This phenomenon is explained by the significant differences in the formation enthalpy values of various species, shifting the equilibria according to the van't Hoff equation, and a significant undercooling in the course of fast freezing of the solution, which enhances the changes of the concentration distribution.

Complexation of 5-fluorosalicylic acid with copper(II): a pH-potentiometric, UV-vis spectroscopic, and electron spin resonance study by the two-dimensional simulation of spectra.

The copper(II)-5-fluorosalicylic acid system was investigated in water and 50 v/v% water-methanol mixture by pH potentiometry combined with UV-vis spectrophotometry, and by the two-dimensional ESR simulation method, respectively. The data revealed that the stable paramagnetic mono- and bis(salicylato) copper(II) complexes [CuLH(-1)] and [CuL2H(-2)](2-) are formed, and at low excess of ligand, the ESR-silent mixed hydroxo complex [Cu2L2H(-3)](-) is also a major species. By the two-dimensional ESR simulation method, the species [CuL]+ in the acidic region, and the minor dimer [Cu2L2H(-2)] were also identified, and the cis and trans isomers of [CuL2H(-2)](2-) were characterized. In frozen solutions, the ESR analysis revealed a slight rhombic distortion of coordination polyhedra for the latter three species.

Molecular distortion effect on ff-emission in a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline.

The electronic and structural behaviour of a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline, [Pr(bathophen)(2)(NO(3))(3)], is investigated with respect to the effect of configuration changes on the Pr(III) centre. [Pr(bathophen)(2)(NO(3))(3)] luminesces from the excited states of the ligand and the metal ion. The fluorescence, ff-emission ((1)D(2)-->(3)H(4)), and phosphorescence bands appear at 394, 608.2 and 482 nm, respectively, in the solid state. In acetonitrile, the complex also shows multiple emissions. From the time-resolved emission and the lifetime measurements, the excitation energy-transfer in [Pr(bathophen)(2)(NO(3))(3)] is clarified, that is, the upper excited triplet level of the ligand acts as an energy donor, while the (1)D(2) levels of Pr(III) is the acceptor. Additionally, the emission phenomena of the complex can be modified by molecular distortion, particularly by rotation of the phenyl groups in the ligand.

catena-Poly[[tetrakis(mu-propionato-kappa(2)O:O')dicopper(II)]-mu-3-pyridylmethanol-kappa(2)N:O-[bis(propionato-kappaO)bis(3-pyridylmethanol-kappaN)copper(II)]-mu-3-pyridylmethanol-kappaO:N].

The title compound, [Cu(3)(C(3)H(5)O(2))(6)(C(6)H(7)NO)(4)](n), is composed of polymeric chains formed by alternating centrosymmetric Cu(2)(mu-CH(3)CH(2)CO(2))(4) and Cu(C(3)H(5)O(2))(2)(C(6)H(7)NO)(2) units. These elemental units are linked by two bridging 3-pyridylmethanol (3PM) ligands. The Cu(2)(mu-CH(3)CH(2)CO(2))(4) group presents a centrosymmetric tetrabridged structure with four syn-syn bridging propionate ligands to which two 3PM molecules are bonded (through N), occupying the apical positions of each square-pyramidal polyhedron around the Cu(II) ions. The remaining mononuclear group is centred around a third Cu(II) ion, which lies on a symmetry centre and is bound to two monodentate propionate groups (through O), two monodentate 3PM molecules (through N) and two bridging 3PM molecules (through O), thus completing a square-bipyramidal CuO(2)N(2)O(2) coordination.