Synthesis, spectral and thermal studies on pyrazolate-bridged palladium(II) coordination polymers

Synthesis, spectroscopic characterization and thermal behavior of pyrazolate-bridged palladium complexes [Pd(mu-Pz)(2)](n) (1), [Pd(mu-mPz)(2)](n) (2), [Pd(mu-dmPz)(2)](n) (3), [Pd(mu-IPz)(2)](n) (4) {pyrazolate (Pz(-)), 4-methylpyrazolate (mPz(-)), 3,5-dimethylpyrazolate (dmPz(-)), 4-iodopyrazolate (IPz(-))} have been described in this work. The exobidentate coordination mode of pyrazolato ligands in 1-4 was inferred on basis of IR spectroscopic evidences. TG investigations indicated that the introduction of substituents at the 4 position in the pyrazolyl moiety into coordination polymers do not affect significantly their thermal stability, whereas at the 3 and 5 position reduced the stability of the main chain. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

THE LEG EXOCRINE SYSTEM IN SERRITERMES-SERRIFER (HAGEN, 1858), PHYLOGENETIC IMPLICATIONS (ISOPTERA, SERRITERMITIDAE

The leg exocrine gland was examined in two species of Neotropical termites. Scanning microscopy studies showed a set of pores on the ventral surface of the first and second tarsomeres in all legs of Serritermes serrifer. In Heterotermes tenuis these pores are present on a sunken plate in all castes. To date, this gland has been observed only in Rhinotermitid species. The presence of leg exocrine gland provides additional evidence supporting a close phylogenetic relationship between the Serritermitidae and Rhinotermitidae.

Attending to the non-preferred hand improves bimanual coordination in children

The effect of attentional focus in bimanual coordination was investigated from a developmental perspective by examining performance of right- and left-handed children, 5-8-years and 9-12-years old, on bimanual reciprocal tapping tasks. Attentional focus was either specified, by asking the children to attend to the preferred or to the non-preferred hand, or unspecified for the execution of the tasks. When attention was oriented to the non-preferred hand we found a reduced movement time and a lower frequency of errors. Performance differences for handedness and age-groups were observed when the children were oriented to attend to the preferred hand or when there was no instruction regarding attention. These differences in performance were eliminated when attention was oriented to the non-preferred hand. (C) 2004 Elsevier B.V. All rights reserved.

Absence of true long-range orbital order in a two-leg Kondo ladder

We investigate, through the density-matrix renormalization group and the Lanczos technique, the possibility of a two-leg Kondo ladder presenting an incommensurate orbital order. Our results indicate staggered short-range orbital order at half-filling. Away from half-filling our data are consistent with incommensurate quasi-long-range orbital order. We also observed that an interaction between the localized spins enhances the rung-rung current correlations.

Head, eye and arm coordination in table tennis

The aim of this study was to determine the role of head, eye and arm movements during the execution of a table tennis forehand stroke. Three-dimensional kinematic analysis of line-of-gaze, arm and ball was used to describe visual and motor behaviour. Skilled and less skilled participants returned the ball to cued right or left target areas under three levels of temporal constraint: pre-, early- and late-cue conditions. In the pre- and early-cue conditions, both high and low skill participants tracked the ball early in flight and kept gaze stable on a location in advance of the ball before ball-bat contact. Skilled participants demonstrated an earlier onset of ball tracking and recorded higher performance accuracy than less skilled counterparts. The manipulation of cue condition showed the limits of adaptation to maintain accuracy on the target. Participants were able to accommodate the constraints imposed by the early-cue condition by using a shorter quiet eye duration, earlier quiet eye offset and reduced arm velocity at contact. In the late-cue condition, modifications to gaze, head and arm movements were not sufficient to preserve accuracy. The findings highlight the functional coupling between perception and action during time-constrained, goal-directed actions.

A 2D coordination polymer with brick-wall network topology based on the [Cu(NCS)(2)(pn)] monomer

The new complex [Cu(NCS)(2)(pn)] (1) (pn = 1,3-propanediamine) has been synthesized and characterized by elemental analysis, infrared and electronic spectroscopy. Single crystal X-ray diffraction studies revealed that complex 1 is made up of neutral [Cu(NCS)(2)(pn)] units which are connected by mu-1,3,3-thiocyanato groups to yield a 2D metal-organic framework with a brick-wall network topology. Intermolecular hydrogen bonds of the type NH...SCN and NH...NCS are also responsible for the stabilization of the crystal structure. (c) 2007 Elsevier B.V. All rights reserved.

Self-assembly of Pd(II) pyrazolyl complexes to 1-D hydrogen-bonded coordination polymers

This work describes the synthesis and characterization of two novel Pd(II) pyrazolyl complexes of the type [PdX2(HdmPz)(2)](n) {X=SCN- (1), N-3(-) (2); HdmPz=3,5-dimethylpyrazole} that self-assemble through N-H...NCS or N-H...NNN hydrogen bonds to yield infinite one-dimensional chains, as confirmed by single crystal X-ray study on 1. The expected solid state polymeric structure for 2 is slowly broken up in CHCl3 Solution, leading to an equilibrium mixture of cis and trans-[Pd(N-3)(2)(HdmPz)(2)] monomers, as demonstrated by time-dependent IR and NMR studies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Environmental coordination chemistry: Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution. Ionic medium effects on equilibrium constants

The molar single activity coefficients associated with propionate ion (Pr) have been determined at 25 degrees C and ionic strengths comprised between 0.300 and 3.00 M, adjusted with NaClO4, as background electrolyte. The investigation was carried out potentiometrically by using a second class Hg/Hg2Pr2 electrode. It was found that the dependence of propionate activity coefficients as a function of ionic strength (I) can be assessed through the following empirical equation: log y(Pr) = -0.185 I-3/2 + 0.104 I-2. Next, simple equations relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous solution, at 25 degrees C, as a function of ionic strength were derived, allowing the interconversion of parameters from one ionic strength to another, up to I = 3.00 M. In addition, thermodynamic formation constants as well as parameters associated with activity coefficients of the complex species in the equilibria are estimated. The body of results shows that the proposed calculation procedure is very consistent with critically selected experimental data.

Spectroscopic study and local coordination of polyphosphate colloidal systems

The interaction between metaphosphate chains and the metal ions Ca2+ and Eu3+ has been studied in water by Eu3+ luminescence, infrared absorption, and P-31 NMR spectroscopy. Two main families of sites could be identified for the metal ions in the aqueous polyphosphate colloidal systems: (1) cagelike sites provided by the polyphosphate chain and (2) a family which arises following saturation of cagelike sites. Occupation of this second family leads to supramolecular interactions between polyphosphate chains and the consequent destabilization of the colloidal system. In the polyphosphate-Ca2+ system, this destabilization appears as a coacervation process. Equilibrium existing between colloidal species as a function of the compositions could be reasoned based on the spectroscopic measurements. The determination of coordination numbers and the correlation of the results with the observation of coacervates show that Eu3+ luminescence properties can be used to probe in a unique way the coacervation process.

Pyrazolyl coordination polymers of cadmium(II)

The coordination polymers [Cd(mu-Cl)(2)(HPz)(2)](n) (1) and [Cd(mu-1,3-SCN)(2)(HPz)(2)](n) (2) (HPz = pyrazole) have been prepared and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction. Both complexes exhibited chain structures made by linear arrays of Cd(II) bridged by chloro (1) or inversely related 1,3-SCN groups (2) and the pyrazole ligands at the apical. sites. Intermolecular hydrogen bonds and another non-covalent interactions are responsible for the self-assembly of linear chains into 2D networks. (c) 2005 Elsevier B.V. All rights reserved.

THERMAL ANALYSES OF COORDINATION-COMPOUNDS .2. THERMAL-DECOMPOSITION OF PALLADIUM COMPLEXES WITH TRIPHENYLPHOSPHINE, TRIPHENYLARSINE AND TRIPHENYLSTIBINE

The compounds [PdCl(2)L(2)] and [PdL(4)] (L=PPh(3), AsPh(3), SbPh(3)) were studied by thermogravimetric and differential thermal analyses in air. The residues of thermal decomposition consist of metallic palladium, except in the case of the complexes containing SbPh(3), when the residues are palladium and antimony mixtures in appropriate proportions with respect to the stoichiometry of the related complexes.