Contribution of solvent effect to the optical spectra of polyanilines: has it been underestimated

The coefficient of thermochromism of polyaniline solutions has been found to be solvent dependent and the solvent effect is not negligible. Hence, thermochromism of polyaniline solutions cannot be explained solely on the basis of conformational change induced by a change in temperature. Further, comparison of the solvatochromism of polyaniline and polytoluidine shows a higher solvatochromic shift for the former. It implies that the higher energy associated with the exciton peak of polytoluidine is not due to the higher ring torsional angle induced by the higher steric repulsion of the methyl group, as widely accepted, but is due to its less solvatochromic red-shift as compared to polyaniline.

Copper( 11) Complexes of Novel Tripodal Ligands containing Phenolate and Benzimidazole/Pyridine Pendants: Synthesis, Structure, Spectra and Electrochemical Behaviour

Mononuclear copper(II) complexes of tri- and tetra-dentate tripodal ligands containing phenolic hydroxyl and benzimidazole or pyridine groups have been isolated. They are of the type (CuL(X)].nH2O, [CuL(H2O)]X.nH2O or [CuL].nH2O where X = Cl-, ClO4-, N3- or NCS- and n = 0-4. The electronic spectra of all the complexes exhibit a broad absorption band around 14000 cm-1 and the polycrystalline as well as the frozen-solution EPR spectra are axial, indicating square-based geometries. The crystal structure of [CuL(Cl)] [HL = (2-hydroxy-5-nitrobenzyl)bis(2-pyridyl-methyl)amine] revealed a square-pyramidal geometry around Cu(II). The mononuclear complex crystallises in the triclinic space group P1BAR with a = 6.938(1), b = 11.782(6), c = 12.678(3) angstrom and alpha = 114.56(3), beta = 92.70(2), gamma = 95.36(2)-degrees. The co-ordination plane is comprised of one tertiary amine and two pyridine nitrogens and a chloride ion. The phenolate ion unusually occupies the axial site, possibly due to the electron-withdrawing p-nitro group. The enhanced pi delocalisation involving the p-nitrophenolate donor elevates the E1/2 values. The spectral and electrochemical results suggest the order of donor strength as nitrophenolate < pyridine < benzimidazole in the tridentate and nitrophenolate < benzimidazole < pyridine in the tetradentate ligand complexes.

Model Based Target Tracking in a Wireless Network of Passive Infrared Sensor Nodes

We consider the problem of tracking an intruder in a plane region by using a wireless sensor network comprising motes equipped with passive infrared (PIR) sensors deployed over the region. An input-output model for the PIR sensor and a method to estimate the angular speed of the target from the sensor output are proposed. With the measurement model so obtained, we study the centralized and decentralized tracking performance using the extended Kalman filter.

Dynamic structure of charge carrier in polyaniline by near-infrared excited resonance Raman spectroscopy

New vibrational Raman features characteristic to the conductive form of polyaniline have been observed with the near-infrared excitation at 1047 nm. Based on an analogy with the resonance Raman spectrum of Michler's ketone in the lowest excited triplet (T-1) state, we consider these features as due to a dynamic structure of a diimino-1,4-phenylene unit in the polyaniline chain exchanging a positive charge very rapidly. This consideration directly leads to a conducting mechanism in which a positive charge migrates from one nitrogen to the other through the conjugated chain of polyaniline.

Synthesis and studies on pyridinium pentafluorozirconate and pyridinium oxotetrafluoroniobate

Pyridinium pentafluorozirconate, (C5H5NH)ZrF5, and pyridinium oxotetrafluoroniobate, (CH5NH)NbOF4, have been synthesised by the reaction of pyridinium poly(hydrogen fluoride), PPHF, with ZrOCl2 and Nb2O5, respectively. These new complexes have been characterised by chemical analysis, thermal analysis, X-ray diffraction and infrared spectra.

C-13 MAS NMR spectra of cis,cis-mucononitrile in liquid-crystalline media and in the solid state. Orientation of the carbon chemical-shift tensors

The spinning sidebands observed in the C-13 MAS NMR spectra of cis,cis-mucononitrile oriented in liquid-crystalline media and of the neat sample in the solid state are studied. There are differences in the sideband intensity patterns in the two cases. These differences arise because the order parameters which characterize the orientation of the solute in the liquid-crystalline media differ for different axes. It is shown that, in general, the relative intensities of the sidebands contain information on the sign and magnitude of an effective chemical-shift parameter which is a function of the sum of the products of the principal components of the chemical-shift tensor and the corresponding order parameters with respect to the director. A method for obtaining the orientation of the carbon chemical-shift tensor is proposed. The carbon chemical-shift tensors obtained from gauge-including atomic orbital calculations are also presented for comparison. (C) 1996 Academic Press, Inc.

Electronic structure of early 3d-transition-metal oxides by analysis of the 2p core-level photoemission spectra

The electronic structures of a wide range of early transition-metal (TM) compounds, including Ti and V oxides with metal valences ranging from 2+ to 5+ and formal d-electron numbers ranging from 0 to 2, have been investigated by a configuration-interaction cluster model analysis of the core-level metal 2p x-ray photoemission spectra (XPS). Inelastic energy-loss backgrounds calculated from experimentally measured electron-energy-loss spectra (EELS) were subtracted from the XPS spectra to remove extrinsic loss features. Parameter values deduced for the charge-transfer energy Delta and the d-d Coulomb repulsion energy U are shown to continue the systematic trends established previously for the late TM compounds, giving support to a charge-transfer mechanism for the satellite structures. The early TM compounds are characterized by a large metal d-ligand p hybridization energy, resulting in strong covalency in these compounds. Values for Delta and U suggest that many early TM compounds should be reclassified as intermediate between the charge-transfer regime and the Mott-Hubbard regime.

Investigation of the L3-M45M45 Auger spectra of Cu, Cu2O and CuO

The authors report a comparative study of the L3-M45M45 Auger spectra of Cu, Cu2O and CuO. The large intensity of the uncorrelated two-hole band-like spectrum in the L3-M45M45 Auger spectra of Cu2O and CuO and the spectral shapes for these transitions indicate strong Cu 3d-O 2p hybridization in the oxides. The L2-L3M45 CK rates obtained for these compounds indicate the stability of the Cu 3d level with increasing oxidation state of Cu. They also provide a quantitative estimate of the contributions of the different processes that lead to the formation of the L3-M45M45 Auger satellite in Cu, Cu2O and CuO.

Preparation, structure, and properties of strontium-doped lanthanum chromites: La1−xSrxCrO3

Strontium-doped lanthanum chromites, La1−xSrxCrO3, have been synthesised to investigate the effect of strontium doping on the stability and physico-chemical characteristics of the perovskite LaCrO3. Both microscopic and X-ray examinations show that the materials exist as single phase perovskite structure for all compositions up to 50 mole% strontium substitution. The materials have been further characterized by infrared and electron paramagnetic resonance spectra. These materials show a good sinterability even in air at 1773 K. Electrical conductivity of thse perovskites has been measured as a function of temperature. Electrical conductivity has been found to be a maximum at x=0.2. The observed electrical and magnetic properties are consistent with activated polaron transport as the mechanism for electrical conduction in these materials.

Structural, optical and EPR studies on ZnO:Cu nanopowders prepared via low temperature solution combustion synthesis

Cu (0.1 mol%) doped ZnO nanopowders have been successfully synthesized by a wet chemical method at a relatively low temperature (300 degrees C). Powder X-ray diffraction (PXRD) analysis, scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) spectroscopy, UV-Visible spectroscopy, Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) measurements were used for characterization. PXRD results confirm that the nanopowders exhibit hexagonal wurtzite structure of ZnO without any secondary phase. The particle size of as-formed product has been calculated by Williamson-Hall (W-H) plots and Scherrer's formula is found to be in the range of similar to 40 nm. TEM image confirms the nano size crystalline nature of Cu doped ZnO. SEM micrographs of undoped and Cu doped ZnO show highly porous with large voids. UV-Vis spectrum showed a red shift in the absorption edge in Cu doped ZnO. PL spectra show prominent peaks corresponding to near band edge UV emission and defect related green emission in the visible region at room temperature and their possible mechanisms have been discussed. The EPR spectrum exhibits a broad resonance signal at g similar to 2.049, and two narrow resonances one at g similar to 1.990 and other at g similar to 1.950. The broad resonance signal at g similar to 2.049 is a characteristic of Cu2+ ion whereas the signal at g similar to 1.990 and g similar to 1.950 can be attributed to ionized oxygen vacancies and shallow donors respectively. The spin concentration (N) and paramagnetic susceptibility (X) have been evaluated and discussed. (C) 2011 Elsevier B. V. All rights reserved.

Structure, Spectra and Redox Behaviour of Copper(11) Complexes of Bis( benzimidazoly1)diamine Ligands

The linear quadridentate ligand N,N'-bis(benzimidazoI-2-ylethyl)ethane-l,2-diamine (L') and its 1 - methylbenzimidazole analogue (L2) and homologues form 1 : 1 complexes with Cu(CIO,),; L' also forms complexes of the types CuL'X, where X = NO,, PF,, Br or CI and CuL'(X)Y where X = CI or Br and Y = CIO, or Br. Deep blue CuL1Br,*2H20 crystallizes in the monoclinic space group C2/c with Z = 4, a = 9.91 9(2), b = 16.626(3), c = 14.1 02(3) le\ and p = 94.39(2)". The structure was solved by Patterson and Fourier difference methods and refined by the least-squares technique to R = 0.064 for 2195 independent reflections with / > 1.50(/). The molecule lies on a two-fold axis symmetrically around Cu". The co-ordination around Cu" is found to be square planar with two amino nitrogens and two benzimidazole nitrogens forming the equatorial plane [CU-N 1.983(3) and 2.037(4) A]. The bromides are at longer distances [3.349(1) A] in axial sites. Ligand field and EPR spectra indicate that one bromide or chloride ion is axially co-ordinated to Cu" in [CuL1l2+. This ion exhibits quasi-reversible redox behaviour. Electrochemical studies of the dihalides in methanol have established the presence of [CuL'X,], [CuL'(X)]+ and [CuL'I2+ in equilibrium. In complexes with 565 [CuL4I2+ [L4 = N,Nbis( benzimidazol-2-ylmethyl)ethane-l,2-diamine] and 555 [CuL3] [L3 = N,N'-bis(1 -methylbenzimidazol- 2-ylmethyl)propane-l,3-diamine] chelate rings, Cull does not seem to lie in the N, square plane, as revealed by their low A values and irreversible electrochemical behaviour. The Cu"-Cu' redox potentials in methanol are in the order [CuL1I2+ < [CuL3I2+ < [CuL4I2+; this illustrates that sixmembered chelate rings are suitable to stabilize Cu", when CU-N 0 interactions are favourable.

Facial Coordination in BIS[BIS(Benzimidazol-2-Ylmethyl)Amine]Copper(II) Perchlorate Dihydrate - Synthesis, Structure, Spectra and Redox Behavior

The 1:1 and 1:2 cooper(II) complexes with the tridentate compound bis(benzimidazol-2-ylmethyl)amine (L(1)) and its benzimidazole (L(2)) and amine (L(3)) N-methyl-substituted derivatives have been prepared and their spectroscopic properties studied. While the 1:1 complexes are of the type CuLX(2) nH(2)O (X = C/O-4(-), NO3-, Cl- or Br-), the 1:2 complexes are of the type CuL(2) (ClO4)(2) nH(2)O (L = L(1) or L(3), n = 0-4). In all these complexes L acts as a tridentate ligand with the amine nitrogen and both the benzimidazole nitrogens co-ordinating to Cu-II. The complex [CuL(2)(1)][ClO4](2) 2H(2)O crystallises in the monoclinic space group P2(1)/c with a = 9.828(2), b = 9.546(2) and c = 19.906(2) Angstrom and beta = 95.71(1)degrees, for Z = 2. The R value is 0.0635 for 2180 significant reflections. The copper(II) ion has an elongated octahedral geometry with four equatorial benzimidazole and two long-distance axial amine N donors. The Cu-N-bzim and Cu-N-amine distances are 2.011(4) and 2.597(6) Angstrom respectively. Factors favouring facial co-ordination to tridentate ligands are discussed. The 1:1 complexes involve meridonal co-ordination of the ligands, with square-based geometry as revealed by ligand-field and EPR spectral properties. The NMe substitution as in CuL(3)(ClO4)(2) confers low V ($) over tilde$$(max) and high E(1/2) for the cu(II)-Cu-I couple. Most of the 1:1 complexes are less reversible but exhibit E(1/2) values more positive than those of the corresponding 1:2 complexes.

Perturbation of the infrared spectrum of lanthanum cobaltate induced by vibronic coupling

Anomalous changes in the infrared intensity of the cobalt-oxygen stretching modes in the infrared spectrum of lanthanum cobaltate (LaCoO3) suggest vibronic coupling. This phenomenon has been studied by infrared vibrational spectroscopy both by temperature-induced changes of spin-state occupation and pressure-induced changes of the crystal field splitting 10Dq.

Reflectivity and photoluminescence spectra of GaAs quantum wells in a magnetic field

We present photoluminescence and reflectance spectra of GaAs/Al-x Ga-1-x As quantum wells in a magnetic field for the Faraday geometry. The photoluminescence peaks recorded are among the most intense and narrow reported to date. This has allowed us to study the behavior of closely spaced bound exciton lines under a magnetic field. Several new features including magnetic field induced splitting of the bound exciton emission peaks are reported.