Comparative Study of Lead(II) Selective Poly(vinyl chloride) Membrane Electrodes Based on Podand Derivatives as Ionophores

The two podand chelates based on diethylsulfide, 1,5‐bis(2′‐hydroxy‐4′‐nitrophenoxy)‐3‐thiapentane (L₁) and 1,5‐bis(8′‐oxybenzopyridine)‐3‐thia pentane (L₂), have been synthesized and explored as neutral ionophores for preparing poly(vinyl chloride) based membrane electrodes selective to Pb²⁺. The addition of anionic additives and various plasticizers has been found to substantially improve the performance of the electrode. The best performance was obtained with the electrode No. 1 having a membrane of ionophore (L₁) with the composition PVC:o‐NPOE:ionophore (L₁):NaTFPB (%w/w) of 33 : 62 : 3 : 2. The electrode exhibits Nernstian response with a slope of 31.57±0.3 mV decade^?1 of activity in the concentration range from 2.0×10^?9 to 1.0×10^?1 M Pb²⁺, performs satisfactorily over a wide pH range (1.6–7.0), with a fast response time (5 s).     

Synthesis, characterization and fluorescence studies of 3,5-diaryl substituted 2-pyrazolines

A series of 2-pyrazolines have been synthesized from α, β unsaturated ketones and hydrazine hydrate with acetic/formic acid in ethanol/DMSO. The structures of 2-pyrazolines have been established by spectroscopic techniques i.e. UV, IR, (1)H NMR, (13)C NMR and micro element analysis. Fluorescence spectra were recorded in the solution at fixed concentration and same excitation wavelength at 290 nm. The absorption band positions of all the compounds broadly lie between 280 and 336 nm and fluorescence band positions in the range between 300 and 370 nm, the near ultraviolet region.     

Luminescence studies and effect of etching on cerium-doped CaS nanoparticles

Cerium-doped calcium sulphide nanoparticles were synthesized using the solid state diffusion method. The formed nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible absorption spectroscopy and photoluminescence (PL) spectroscopy. The XRD pattern confirmed a cubic CaS phase with an average grain size of 53 nm of the formed samples. The TEM image showed non-agglomerated particles with an average size of 60 nm, which is in close agreement with the XRD result. The PL-emission spectrum showed peaks at 506 and 565 nm due to the transition from the excited state to the ground state of Ce³⁺. The effect of etching has been studied on the luminescent properties of CaS:Ce phosphors. With an increase in the etching time there is decrease in the size of the particles, as a result of which the PL spectrum showed a slight blue shift. The UV-visible absorption spectrum also showed a blue shift with an increase in etching time, which is in agreement with the nanosize effect.     

Synthesis characterization and hydroformylation activity of new mononuclear rhodium(I) compounds incorporated with polar-group functionalized phosphines

A first effort employing a range of polar-group functionalized phosphines (L ₁ –L ₇ ) to design mononuclear Rh(I) compounds of [Rh(quin-8-O)(CO)(L)] (quin-8-O = 8-hydroxy quinolate) is described. The reaction of a Rh(I) precursor [Rh(μ-Cl)(CO)₂]₂ with 8-hydroxyquinoline in the presence of a base followed by phosphines (L ₁ –L ₇ ) produced only a single isomer of [Rh(quin-8-O)(CO)(L)] compounds (1–7) with pendant, i.e. non-bonded, polar-groups (includes carboxyl, hydroxyl and formyl). A relationship between Δgd³¹P chemical shifts and the ν(C≡O) was derived to evaluate and explain the σ-donor properties of these phosphines with respect to the electronic properties of the polar groups and the extent of π-back-bonding to the CO group. These mononuclear Rh(I)-Phosphines were investigated as catalysts in the hydroformylation of 1-hexene and cyclohexene in aqueous two-phase and single-phase solvent systems. The Rh(I) catalysts with strong σ-donor and hydrophilic phosphines provided better yields and selectivities for the hydroformylation products, which is a reverse trend compared to literature reports. When the Rh(I) compounds contained strong σ-donor phosphines, the π-acceptor properties of the pyridine ring of 8-hydroxyquinolate were found to be beneficial for the facile cleavage of the CO group during hydroformylation, and additionally, to improve the kinetic stability of catalysts.     

Synthesis and Characterization of Hexathiophenes with Methylthienyl Side Chains

Summary: Two novel conjugated isomeric hexathiophenes 6T1 and 6T2 bearing 5-methyl-2-thienyl substituents have been synthesized by Suzuki coupling and oxidative dimerization method. These isomers were characterized by ¹H NMR, ¹³C NMR, elemental and mass analysis. The two hexamers show good solubility in common solvents and show almost identical UV-vis absorption spectra in solution with a maximum cantered at 387 nm. These materials bearing thienyl substituents in the sidechain are anticipated to provide better charge transport in devices and hold promise for use in organic field effect transistors.     

Force constant variation from crystalline to amorphous germanium

The phonon density of states for crystalline germanium (cz.sbnd;Ge) and amorphous germanium (aGe) have been computed by means of de Launay angular force model, considering only the first nearest neighbour interactions. The relevancy of computed phonon density of states to the interpretation of infrared and Raman spectra of az.sbnd;Ge are discussed, and the decrease in force constants of the order of 10% has been observed when the phase changes from crystalline to amorphous state.     

Engineering the nonlinear phase shift

We treat the nonlinear phase shift response in the weak perturbation limit as a linear digital filter that can be synthesized into the values of its poles and zeros and mapped onto an optical architecture. This procedure results in a significant enhancement in the nonlinear sensitivity with a response that is robust to frequency changes within the filter passband. A precompensation technique can be used to reduce distortions under strongly driven nonlinear operation to achieve a larger phase shift. We also show that nonlinear sensitivity improves with increasing filter group delay and can be increased within constant linear bandwidth by use of higher-order filters.     

The influence of substituents (R) at the C carbon on bonding properties of thiosemicarbazones {RC(H)N-NH–C(S)–NH2} in palladium(II) complexes

Reactions of the trans-PdCl₂(PPh₃)₂ precursor with furan-2-carbaldehyde thiosemicarbazone (Hftsc) and thiophene-2-carbaldehyde thiosemicarbazone (Httsc), in 1:1 molar ratios in the presence of Et₃N base, removed one Cl and one PPh₃ group from the Pd^II center, and yielded the complexes [Pd(η²-N³,S-ftsc)(PPh₃)Cl] (1) and [Pd(η²-N³,S-ttsc)(PPh₃)Cl] (2), respectively. However, when a 1:2 molar ratio (M:L) was used, both Cl and PPh₃ ligands were removed, yielding the complexes trans-[Pd(η²-N³,S-ftsc)₂] (3) and trans-[Pd(η²-N³,S-ttsc)₂] (4). Complexes 1–4 have been characterized with the help of analytical data, spectroscopic techniques (IR, ¹H and ³¹P NMR) and single crystal X-ray crystallography. The thiosemicarbazone ligands behave as uninegative N³,S-chelating ligands in complexes 1–4. In contrast, pyrrole-2-carbaldehyde thiosemicarbazone (H₂ptsc) and salicylaldehyde thiosemicarbazone (H₂stsc) invariably formed the complexes [Pd(η³-N⁴,N³,S-ptsc)(PPh₃)] (5) and [Pd(η³–O, N³,S-stsc)(PPh₃)] (6), respectively, and the ligands acted as binegative tridentate donors (N⁴, N³, S, 5; O, N³, S, 6).     

Synthesis,characterization and structures of copper(II) complexes with amide-based ligands: Unusual formation of a linear trimer and a zig-zag chain and their contrast magnetic behaviour

The present work illustrates the versatile coordination modes of the amide-based ligands towards copper(II) ion. The reaction of the deprotonated form of the ligand, [L¹]²⁻ with CuCl₂ affords a linear trinuclear complex, [Cu₃(L¹)₂(Cl)₂(H₂O)] (1) which has been characterized thoroughly including single crystal structure analysis. The structure of 1 shows that one of the arm of the flexible ligand flips to coordinate second copper(II) centre, resulting in the formation of a trinuclear complex. On the other hand, ligand H₂L² in its deprotonated form reacts with Cu(II) ion to give complex 2 with general formula, [Cu(L²)]_n (2). The crystal structure of the complex 2 shows that each copper is square-pyramidal with 5th coordination coming from the O-atom of the amide group from a neighbouring complex. This results in the generation of an one-dimensional zig-zag chain. The variable temperature magnetic measurements of the complexes, 1 and 2 show that while Cu ions in the former are antiferromagnetically coupled (J = −110.34 cm⁻¹), a weak ferromagnetic interaction (J = +3.08 cm⁻¹) exists in the later. A rationale, based on the orbital overlap from the copper ions and associated ligands, is provided for the observed magnetic coupling between the copper ions.