Synthesis and characterization of single-source molecular precursors for the preparation of metal chalcogenides

Metal chalcogenides constitute an important family of functional materials. Subtle changes in shape, size and phase of these materials result in variations in physical properties (e.g. electronic and optical), which can be exploited for various technological applications. Several strategies have evolved recently for controlling shape, size and phase of these materials. This work discusses design and synthesis of single-source molecular precursors for the preparation of metal chalcogenides both in bulk and nano-size regime. Precursors for palladium chalcogenides, indium sulphides andII–VI materials are presented. Synthesis of a variety of palladium(II)/platinum(II) complexes with internally functionalised chalcogenolate ligands, selenocarboxylates; gallium and indium dithiolate complexes and zinc/cadmium/ mercury complexes with N,N′-dimethylaminoalkylselenolate ligands and their characterization by NMR and X-ray crystallography are also discussed. Data on thermal behaviour of a few representative complexes, [Pd(SeCOAr)₂(PR₃)₂], [PdCl(E∩N)(PR₃)], [InMe₂(S∩S)], [In(S∩S)₃] and [M(E(CH₂)_nNMe₂)₂] (M = Zn, Cd, Hg;n = 2 or 3) are presented.     

Fixed-bed study for adsorptive removal of furfural by activated carbon

In our previous study [A.K. Sahu, V.C. Srivastava, I.D. Mall, D.H. Latye, Sep. Sci. Technol. 43 (5) (2008) 1239], commercial grade activated carbon (ACC) was used for adsorptive removal of furfural from aqueous solution using batch studies. In the present study, continuous fixed-bed adsorption was carried out in ACC packed bed for the removal of furfural from aqueous solution. The effects of important factors namely bed height (Z = 15–60 cm), influent concentration of furfural (C_o = 50–200 mg/l), the flow rate (Q = 0.02–0.04 l/min) and column diameter (D = 2–4 cm) were studied. Capacity of the bed to adsorb furfural was found to increase with an increase in the value of Z, C_o and D; and with decrease in the value of Q. Adams–Bohart, Bed-Depth Service-Time, Thomas, Yoon–Nelson, Clark and Wolborska models were applied to the experimental data for the prediction of the breakthrough point, and to determine the characteristic parameters of the column. Error analysis showed that the Yoon–Nelson model best described the experimental breakthrough curve, while Wolborska model showed good prediction of breakthrough curve for the relative concentration region up to 0.5.     

Isolation of chloro-bridged arylpalladium complexes, [Pd2Ar2(μ-Cl)2(PR3)2], in palladium catalyzed C–C cross coupling reaction of triarylbismuth with arylhalides

The reaction of [Pd₂Cl₂(μ-Cl)₂(PR₃)₂] with triarylbismuth in dichloromethane at room temperature afforded chloro-bridged arylpalladium complexes, [Pd₂Ar₂(μ-Cl)₂(PR₃)₂] (Ar = Ph or 4-MeC₆H₄ (tol)) in 85–90% yield as a yellow crystalline powder. These complexes were characterized by elemental analysis and NMR spectroscopy. Molecular structures of [Pd₂tol₂(μ-Cl)₂(PEt₃)₂] and [Pd₂Ph₂(μ-Cl)₂(PMePh₂)₂] were established by single crystal X-ray crystallography. These complexes are centrosymmetric dimers with trans configuration. The C–C coupling reaction between triarylbismuth and an arylhalide in the presence of a base is catalyzed by [Pd₂Cl₂(μ-Cl)₂(PR₃)₂]. The reactions proceed via an arylpalladium complex formed by transmetallation reaction between [Pd₂Cl₂(μ-Cl)₂(PR₃)₂] and Ar₃Bi. Probable reaction routes for C–C coupling have been discussed.     

Binuclear Orthometalated N,N-Dimethylbenzylamine Complexes of Palladium(II): Synthesis,Structures and Thermal Behavior

Abstract

Organochalcogenolate-bridged cyclometalated palladium(II) complexes of the formulae, [Pd₂(μ-Epy)₂(Me₂NCH₂C₆H₄-C,N)₂] (2) (E = S (2a), Se (2b)), [Pd₂(μ-SAr)(μ-Cl)(Me₂NCH₂C₆H₄-C,N)₂] (3) (Ar = Ph (3a), Mes (Mes = 2,4,6-Me₃C₆H₂) (3b)) and [Pd₂(μ-SeAr)₂(Me₂NCH₂C₆H₄-C,N)₂] (4) (Ar = Ph (4a), Mes (4b)), have been synthesized by the reactions of [Pd₂(μ-Cl)₂(Me₂NCH₂C₆H₄-C,N)₂] with lead or sodium salts of the chalcogenolate ligand. These complexes have been characterized by elemental analysis, mass spectral data, and NMR (¹H and ⁷⁷Se{¹H}) spectroscopy. The molecular structure of 2, determined by single crystal X-ray diffraction analysis, revealed a Epy-bridged head-to-tail arrangement in which the eight-membered “(PdECN)₂” ring adopts a distorted twist boat conformation. The Pd····Pd separation in 2a is within the van-der-Waals interaction but in 2b it is too large to support the presence of any metal–metal interaction. The thermal behavior of these complexes has been studied by thermogravimetric analysis.     

Laser-induced thermal lens study of the role of morphology and hydroxyl group in the evolution of thermal diffusivity of copper oxide

The paper explores the evolution of thermal behavior of the material by studying the variations in thermal diffusivity using the single beam thermal lens (TL) technique. For this purpose, the decomposition of Cu(OH)₂ into CuO is studied in a time range up to 120 h, by subjecting the sample to morphological, structural, and spectroscopic characterizations. The time evolution of thermal diffusivity can be divided into three regions for demonstrating the dynamics of the reaction. When the reaction is complete, the thermal diffusivity is also found to be saturated. In addition to the morphological modifications, from rods to flakes, the variations in the amount of hydroxyl group are attributed to be responsible for the enhancement of base fluid's thermal diffusivity by 165%. Thus the study unveils the role of hydroxyl groups in the thermal behavior of CuO.     

Synthesis of new tripodal receptors—a ‘PET’ based ‘off-on’ recognition of Ag

A new set of tripodal receptors based upon an aromatic platform have been synthesized in high yields. The compounds have been characterized by spectroscopic techniques and by single crystal X-ray crystallography. These receptors are found to have good extraction ability and high transport rate for Ag(I). The receptor with imine linkages exhibits weak fluorescence emission bands at λ_max=413 and 540 nm, upon excitation at λ_max=365 nm. The fluorescence spectrum of the receptor shows enhancement in the intensity of the signal at 413 nm on binding with the Ag⁺ cation. No such significant changes are observed with other metal ions. An absorption at ∼365 nm is typical of an intraligand (π-π^∗) transition involving the imine chromophore, which produces a weak emission band at 413 nm due to quenching caused by PET from a neighboring -OH group. Participation of OH group in coordination to the metal ion reduces PET and an enhancement of fluorescence intensity is observed, signaling recognition of the metal ion.     

Structural basis for unusually long wavelength charge transfer transitions in complexes [MCl(ECH(2)CH(2)NMe(2))(PR(3))] (E = Te,Se; M = Pt,Pd): experimental results and TD-DFT calculations

A series of new complexes, the blue compounds [PdCl(TeCH(2)CH(2)NMe(2))(PR(3))] (PR(3) = PEt(3), PPr(n)(3), PBu(n)(3), PMe(2)Ph, PMePh(2), PPh(3), PTol(3)) and the red [PtCl(TeCH(2)CH(2)NMe(2))(PR(3))] (PR(3) = PMe(2)Ph, PMePh(2)), were synthesized and studied spectroscopically ((1)H and (31)P NMR, UV/vis) and by cyclic voltammetry. The structures of [PdCl(TeCH(2)CH(2)NMe(2))(PPr(n)(3))] (2b) [PdCl(TeCH(2)CH(2)NMe(2))(PMePh(2))] (2e), [PtCl(TeCH(2)CH(2)NMe(2))(PMePh(2))] (2i), and the related [PtCl(SeCH(2)CH(2)NMe(2))(PEt(3))] (3) were determined crystallographically, revealing a typical pattern of trans-positioned neutral N and P donor atoms in an approximately square planar setting. The molecules 2b, 2e, and 2i were calculated by TD-DFT methodology to understand the origin of the weak (epsilon approximately 200 M(-1) cm(-1)) long-wavelength bands at about 600 nm for Pd/Te complexes such as 2b or 2e, at ca. 460 nm for Pt/Te systems such as 2i, and at about 405 nm for Pt/Se analogues such as 3. These transitions are identified as charge transfer transitions from the selenolato or tellurolato centers to unoccupied orbitals involving mainly the phosphine coligands for the Pt(II) compounds and more delocalized MOs for the Pd(II) analogues. Calculations and electrochemical data were used to rationalize the effects of metal and chalcogen variation.     

Diorgano-gallium and -indium complexes with N-heterocyclic carboxylic acids: Synthesis, characterization and structures of [Me2M(O2C-C5H4N)]2, M = Ga or In

The reaction of triorgano-gallium and -indium etherate with heterocyclic carboxylic acids in benzene at room temperature yields complexes of the type [R₂M(L)]_n(M = Ga or In; R = Me or Et; L = 2-(C₅H₄N)CO₂, 2-(C₄H₃N₂)CO₂ or 2-(C₉H₆N)CO₂). These complexes have been characterized by elemental analysis, IR, UV-vis, NMR (¹H and ¹³C{¹H}) and mass spectral data. Complexes with L = (C₅H₄N)CO₂- and (C₉H₆N)CO₂- showed photoluminescence on excitation with ∼250 or ∼310 nm radiation, respectively. Single crystal X-ray structural analysis of [Me₂M(O₂C-C₅H₄N-2)]₂ (M = Ga or In), revealed a dimeric structure with five-coordinate metal atoms arising from the presence of two tridentate bridging picolinate ligands.     

Experimental and ab initio dynamical investigations of the kinetics and intramolecular energy transfer mechanisms for the OH + 1,3-butadiene reaction between 263 and 423 K at low pressure

The rate constants for the reaction of the OH radical with 1,3-butadiene and its deuterated isotopomer has been measured at 1-6 Torr total pressure over the temperature range of 263-423 K using the discharge flow system coupled with resonance fluorescence/laser-induced fluorescence detection of OH. The measured rate constants for the OH + 1,3-butadiene and OH + 1,3-butadiene- d 6 reactions at room temperature were found to be (6.98 +/- 0.28) x 10 (-11) and (6.94 +/- 0.38) x 10 (-11) cm (3) molecule (-1) s (-1), respectively, in good agreement with previous measurements at higher pressures. An Arrhenius expression for this reaction was determined to be k 1 (II)( T) = (7.23 +/- 1.2) x10 (-11)exp[(664 +/- 49)/ T] cm (3) molecule (-1) s (-1) at 263-423 K. The reaction was found to be independent of pressure between 1 and 6 Torr and over the temperature range of 262- 423 K, in contrast to previous results for the OH + isoprene reaction under similar conditions. To help interpret these results, ab initio molecular dynamics results are presented where the intramolecular energy redistribution is analyzed for the product adducts formed in the OH + isoprene and OH + butadiene reactions.     

Treatment of pulp and paper mill wastewaters with poly aluminium chloride and bagasse fly ash

The present study deals with the use of poly aluminium chloride (PAC) as a coagulant and bagasse fly ash (BFA), which is generated in sugar mills, as an adsorbent for the removal of chemical oxygen demand (COD) and colour of pulp and paper mill effluents. Under optimal conditions of pH 3 and initial PAC dosage of 3 g/l, about 80% COD removal and 90% colour removal were obtained. The optimal conditions for the adsorptive removal of COD and colour with BFA were pH 4 and BFA dosage of 2 g/l. Under these conditions, COD and colour removal were, respectively, 50 and 55%. Adsorptive removal of COD by BFA followed second-order kinetics. Intra-particle diffusion was found to be rate controlling. Freundlich and Langmuir adsorption isotherms were found to fit the equilibrium adsorption data with BFA. Two-stage treatment using PAC (3 g/l) as a coagulant in the first stage and BFA (2 g/l) as an adsorbent in the second stage gave the combined COD and colour removal of nearly 87 and 95%, respectively, for different effluents without any pH adjustment. Two-stage adsorptive treatment using BFA (2 g/l) in both the stages gave a combined COD and colour removal of about 70%. The sludge obtained can be dewatered by centri-clarifiers, dried, briquetted and incinerated to recover its energy content.