Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

Effect of a methyl group on the spontaneous resolution of a square-pyramidal coordination compound: crystal packing and conglomerate formation

Reaction of [Cu(pic)2]·2H2O (where pic stands for 2-picolinato) with 2-({[2-(dimethylamino)ethyl]amino}methyl)phenol (HL1) produces the square-pyramidal complex [CuL1(pic)] (1), which crystallizes as a conglomerate (namely a mixture of optically pure crystals) in the Sohncke space group P212121. The use of the methylated ligand at the benzylic position, i.e. (±)-2-(1-{[2-(dimethylamino)ethyl]amino}ethyl)phenol (HL2), yields the analogous five-coordinate complex [CuL2(pic)] (2) that crystallizes as a true racemate (namely the crystals contain both enantiomers) in the centrosymmetric space group P21/c. Density functional theory (DFT) calculations indicate that the presence of the methyl group indeed leads to a distinct crystallization behaviour, not only by intramolecular steric effects, but also because its involvement in non-covalent C–H···π and hydrophobic intermolecular contacts appears to be an important factor contributing to the crystal-lattice (stabilizing) energy of 2

An inductor-free realization of the Chua`s circuit based on electronic analogy

Although literature presents several alternatives, an approach based on the electronic analogy was still not considered for the implementation of an inductor-free realization of the double scroll Chua`s circuit. This paper presents a new inductor-free configuration of the Chua`s circuit based on the electronic analogy. This proposal results in a versatile and functional inductorless implementation of the Chua`s circuit that offers new and interesting features for several applications. The analogous circuit is implemented and used to perform an experimental mapping of a large variety of attractors.

Performance evaluation on electronic control systemsfor field sprayers using programmable logic controllers

The aim of this study was to develop a laboratory method for time response evaluation on electronically controlled spray equipment using Programmable Logic Controllers (PLCs). For that purpose, a PLC controlled digital drive inverter was set up to drive an asynchronous electric motor linked to a centrifugal pump on a experimental sprayer equipped with electronic flow control. The PLC was operated via RS232 serial communication from a PC computer. A user program was written to control de motor by adjusting the following system variables, all related to the motor speed: time stopped; ramp up and ramp down times, time running at a given constant speed and ramp down time to stop the motor. This set up was used in conjunction with a data acquisition system to perform laboratory tests with an electronically controlled sprayer. Time response for pressure stabilization was measured while changing the pump speed by +/-20%. The results showed that for a 0.2 s ramp time increasing the motor speed, as an example, an AgLogix Flow Control system (Midwest Technologies Inc.) took 22 s in average to readjust the pressure. When decreasing the motor speed, this time response was down to 8 s. General results also showed that this kind of methodology could make easier the definition of standards for tests on electronically controlled application equipment.

Effect of age and genetic group on characteristics of the scrotum, testes and testicular vascular cones, and on sperm production and semen quality in AI bulls in Brazil

The objectives were to determine the effects of age and genetic group on characteristics of the scrotum, testes and testicular vascular cones (TVC), and on sperm production and semen quality in 107 Bos indicus, B, taurus and cross-bred bulls at three artificial insemination (AI) centers in Brazil. In addition, predictors of sperm production and semen quality were identified. In general, scrotal circumference (SC), scrotal shape score, scrotal neck perimeter, and testicular size (length, width and volume) increased (P < 0.05) with age. Although there were no significant differences among genetic groups for SC or testicular size, B. indicus bulls had the least pendulous scrotal shape, the shortest scrotal neck length, and the greatest scrotal neck perimeter (P < 0.05). Fat covering the TVC was thinner (P < 0.05) in bulls <= 36 months of age and in B. taunts bulls than in older bulls and B. indicus bulls, respectively. Age and genetic group did not affect testicular ultrasonic echotexture. B. indicus bulls tended (P < 0.1) to have the lowest average scrotal surface temperature (SST). In general, ejaculate volume, total number of spermatozoa and number of viable spermatozoa increased (P < 0.05) with age. However, there was no significant effect of age on sperm concentration, motility, major and total defects. The proportion of spermatozoa with minor defects was highest (P < 0.05) in bulls 37-60 months of age. B. indicus bulls had higher (P < 0.01) sperm concentration, total number of spermatozoa and number of viable spermatozoa than B. taunts bulls, with intermediate values for cross-bred bulls. Increased sperm production was associated with increased testicular volume, SC, TVC fat cover, and SST top-to-bottom gradient. Decreased semen quality was associated with increased SC and bottom SST, and decreased scrotal shape, scrotal neck perimeter and vascular cone diameter. In summary, age and genetic group affected the characteristics of the scrotum, testes, and TVC, sperm production and semen quality. In addition, characteristics of the scrotum, testes and TVC were associated with sperm production and semen quality in bulls and could be assessed for breeding soundness evaluation. (c) 2002 Elsevier B.V. All rights reserved.

A theoretical analysis on electronic structure of the (110) surface of TiO2-SnO2 mixed oxide

Mixed oxide compounds, such as TiO2-SnO2 system are widely used as gas sensors and should also provide varistor properties modifying the TiO2 surface. Therefore, a theoretical investigation has been carried out characterizing the effect of SnO2 on TiO2 addition on the electronic structure by means of ab initio SCF-LCAO calculations using all electrons. In order to take into account the finite size of the cluster, we have used the point charge model for the (TiO2)(15) cluster to study the effect on electronic structure of doping the TiO2 (110) Surface. The contracted basis set for titanium (4322/42/3), oxygen (33/3) and tin (43333/4333/43) atoms were used. The charge distributions, dipole moments, and density of states of doping TiO2 and vacancy formation are reported and analysed. (C) 2003 Elsevier B.V. All rights reserved.

Report on the coordination of international statistical activities in the area of the environment

Includes bibliography.