Mercury Thiocyanate Research Articles

Growth of manganese doped cadmium mercury thiocyanate single crystals — Gel technique

Some of the doped crystals of bimetallic thiocyanate complexes are found to exhibit excellent nonlinear optical properties. Manganese doped cadmium mercury thiocyanate single crystals of appreciable size have been obtained from silica gel by the process of diffusion. The X-ray diffraction studies show the crystal lattice to be tetragonal revealing that doping does not alter the structure of the parent crystal. To study the crystalline perfection of the grown crystals, high resolution X-ray diffraction analysis was carried out. Being a nonlinear crystal, Kurtz powder test was carried out to confirm its second harmonic generation efficiency. The results are discussed in comparison with pure CMTC.

Growth of cadmium mercury thiocyanate single crystals using acetone–water mixed solvent and their characterization studies

Cadmium mercury tetrathiocyanate single crystals were grown from acetone–water (4:1) mixed solvent by slow evaporation solution technique. The structure of the grown crystal was confirmed by single-crystal X-ray diffraction analysis. The crystalline perfection of cadmium mercury thiocyanate (CMTC) was ascertained by high-resolution X-ray diffraction (HRXRD) analysis. The presence of functional groups and the coordination of thiocyanate ion in the CMTC compound were confirmed by laser Raman spectroscopy. The optical transparency of CMTC single crystal was studied by UV–vis spectroscopy. Single-shot surface laser damage threshold of CMTC estimated using an Nd-YAG laser of wavelength 1064 nm was found to be 4.59 GW/cm 2 and second harmonic generation (SHG) output power was estimated through the Kurtz powder method. Dielectric constant and dielectric loss for various frequencies and temperatures were performed on CMTC single crystal.

Comparative study of pure and alkaline earth metallic doped cadmium mercury thiocyanate single crystals—Gel technique

Growth aspects of Ba and Ca doped cadmium mercury thiocyanate (CMTC) single crystals from silica gel by the process of diffusion are discussed. The incorporation of dopants in the crystal has been confirmed by inductively coupled plasma (ICP) analysis. Single crystal X-ray diffraction studies reveal the structures of the doped crystals to be tetragonal implying that the incorporation of the dopants has not changed the structure of the parent crystal. The diffraction planes were identified and indexed by powder diffraction analysis. High-resolution X-ray diffraction analyses were carried out to investigate the crystalline perfection of the grown crystals. The grown crystals were characterized by Fourier transform infrared and transmission spectral analyses. Vickers microhardness studies on the grown crystals reveal that they belong to soft material category. Employing powder Kurtz method, their second harmonic generation efficiencies were measured in comparison with urea.

GROWTH MODES AND DEFECTS OF MANGANESE MERCURY THIOCYANATE CRYSTALS OBSERVED BY AFM

Growth mechanisms and defects formation of the manganese mercury thiocyanate (MMTC) crystal have been investigated by atomic force microscopy (AFM). Both screw dislocation controlled growth and 2D nucleation growth occur on the {110} faces. Stacking faults are observed among dislocation hillocks and the formation of them probably results from the different crystallization orientations of different spirals. Hollow channels are found around the nucleation islands and the formation of them is due to the instability of the interface generated by the rapid nucleation and growth speeds.

A comparative study of pure and potassium doped cadmium mercury thiocyanate single crystals grown in silica gel

AbstractPure and potassium doped cadmium mercury thiocyanate single crystals have been obtained from silica gel by the process of diffusion. The X‐ray diffraction studies reveal the crystal lattice of both pure and doped crystals to be tetragonal. The crystalline perfection of the grown crystals were investigated by high resolution X‐ray diffraction analysis and the quality of the crystals are found to be extremely good. Transmission and Fourier transform infrared spectra were recorded for the grown crystals. The TG/DTA analyses show that the crystals are highly thermally stable. The mechanical strength of the crystals were studied by Vickers microhardness test and a study of their second harmonic generation efficiency in comparison with urea has been made by performing Kurtz powder test. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Transition metal complexes with pyrazole-based ligands, Part 29: Reactions of zinc(II) and mercury(II) thiocyanate with 4-acetyl-3-amino-5-methylpyrazole

The work is concerned with the crystal and molecular structures of zinc(II) and mercury(II) complexes with 4-acetyl-3-amino-5-methyl-pyrazole (aamp) of the coordination formulae [Zn(NCS)2(aamp)2[ and (Haamp)2[Hg(SCN)4]. The zinc(II) complex was obtained by the reaction of a warm methanolic solution of aamp with a mixture of zinc(II) nitrate and ammonium thiocyanate, whereas the mercury(II) complex was prepared by the reaction of a warm ethanolic solution of aamp and a warm, slightly acidified aqueous solution of [Hg(SCN)4]2-. Both complexes have a tetrahedral geometry, which in the case of zinc complex is formed by monodentate coordination of two aamp molecules and two isothiocyanate groups. The Zn(II) and Hg(II) atoms have significantly deformed coordination geometry. In both crystal structures the pyrazole derivative has a planar form, probably stabilized by an intramolecular N-H???O hydrogen bond. Apart from the X-ray structural analysis, the isolated complexes were characterized by elemental analysis, IR spectroscopy, conductometric measurements and thermal analysis.

Novel rare case of 2D + 1D = 2D polycatenation Hg(ii) coordination polymer

A novel polymeric mercury(II) thiocyanate coordination polymers, [Hg2(µ-bpdh)(µ-SCN)4]n[Hg2(µ-bpdh)(µ-SCN)4]2n (1) (bpdh = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene) was prepared and fully characterized. In compound 1, the bridging ligand bpdh adopts a trans-oid conformation and the network contains two interpenetrating coordination polymers, a 2D net and a 1D double chain, which results in a very rare case of 2D + 1D = 2D polycatenation.

Spectroscopic, thermal and structural studies of a new mercury(II) complex of 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (pyterpy) ligand, [Hg (hpyterpy)(SCN)2]2(MeSO4)2

A new mercury(II) complex [Hg(Hpyterpy)(SCN)2]2(MeSO4)2 was prepared from the reaction of 4′-(4-pyridyl)-2,2′:6′,2″- terpyridine (pyterpy), as a polypyridyl ligand, with mercury(II) thiocyanate. The compound was characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy and its structure was determined by X-ray single-crystal diffraction. The thermal stability of compound was studied by thermogravimetric (TG) and differential thermal analyses (DTA).

Studies on the electrical, linear and nonlinear optical properties of Manganese mercury thiocyanate bis-dimethyl sulfoxide, an efficient NLO crystal

Abstract Manganese mercury thiocyanate bis-dimethyl sulfoxide (MMTD), a novel organo-metallic nonlinear optical (NLO) crystal, was grown by a slow evaporation technique over a period of 30 days. The grown crystal was subjected to single crystal X-ray diffraction to determine the unit cell parameters. The optical properties of MMTD were investigated by UV–Vis–NIR, FTIR and FT-Raman spectroscopic techniques. The second harmonic generation (SHG) efficiency of the sample was measured using a Q-switched, mode-locked Nd:YAG laser and the results were compared with urea and manganese mercury thiocyanate (MMTC). The thermal parameters, such as the thermal diffusivity ( α ), thermal effusivity ( e ), thermal conductivity ( k ) and heat capacity ( c p ) of MMTD were measured by the photopyroelectric (PPE) technique and the results are discussed. The dielectric response and mechanical properties of MMTD have also been investigated and reported.

Nucleation kinetics and growth of nonlinear optical bis (dimethyl sulfoxide) manganese mercury thiocyanate single crystals

AbstractNonlinear optical (NLO) material of bis (dimethyl sulfoxide) manganese mercury thiocyanate (MMTD) was synthesized by two step reaction method. The solubility and metastable zonewidth were experimentally determined in order to optimize the growth parameters. Bulk crystals of MMTD were grown by slow cooling and slow evaporation methods. The structure of the grown crystal was confirmed by X‐ray diffraction analysis. Presence of functional groups and the coordination of Lewis base ligand of dimethyl sulfoxide (DMSO) were confirmed by FT‐IR analysis. Optical transparency of the grown crystals was studied by UV‐Vis spectroscopy. Nonlinear optical property of the grown crystal was confirmed by Kurtz powder method. Etching studies reveal the formation of triangular hillock etch patterns, indicative of 2D nucleation mechanism. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Growth and characterization of nonlinear optical bis-(dimethylsulfoxide) cadmium mercury thiocyanate single crystal

Effect of pH on the stability of aqueous solution and growth kinetics of bis-(dimethylsulfoxide) cadmium mercury thiocyanate has been investigated. The solubility was estimated for the optimized pH value of 3.5. Bulk single crystals were grown from mixed solution of water:dimethylsulfoxide (3:1) by slow cooling and slow evaporation methods under the optimized pH value. The structure and morphology of the grown crystal was confirmed by single crystal X-ray diffraction analysis. Presence of functional groups and the coordination of dimethylsulfoxide to the parent compound of cadmium mercury thiocyanate were confirmed through Fourier transform-infrared spectroscopy and further they were confirmed by laser Raman spectroscopic analysis. Optical transparency of the grown crystal was observed by UV–visible spectroscopy. The thermal stability and thermal decomposition of cadmium mercury thiocyanate (CMTD) single crystals were investigated by means of thermo gravimetric analysis, differential thermal analysis and differential scanning calorimetric analysis. The nonlinear optical efficiency of the grown crystal was estimated by Kurtz powder method.

Spectroscopic, thermal and structural studies of a new mercury(II) one-dimensional coordination polymer, [Hg(3-bpo)2(SCN)2], 3-bpo = 2,5- bis (3-pyridyl)-1,3,4-oxadiazole

A new mercury(II)-organic polymeric complex generated from 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) as an angular dipyridyl derivative ligand, [Hg(3-bpo)2(SCN)2], was prepared from reactions of ligand 3-bpo with mercury(II) thiocyanate. The compound was characterized by elemental analysis, IR-, 1H NMR-, 13C NMR-spectroscopy and structurally determined by X-ray single crystal diffraction. The thermal stability of [Hg(3-bpo)2(SCN)2] was studied by thermal gravimetric (TG) and differential thermal analyses (DTA).

Synthesis, growth and characterization analysis of nickel mercury thiocyanate crystal (NMTC)

The nonlinear optical single crystal of NiHg(SCN) 4 has been successfully synthesized and good quality single crystal has been grown by slow cooling solution growth technique. The grown single crystals have been analyzed by different characterization analyses in order to know its suitability for various applications. The functional groups have been identified from the FTIR analysis. The TG/DTA analysis reveals the thermal behavior of NMTC. The optical behaviour was assessed by UV–Vis analysis and was found with no absorption in the entire visible region and it may be useful for second harmonic and other relevant applications. The relative second harmonic generation efficiency was evaluated by Kurtz powder technique and was found to be good in comparison with the standard inorganic potassium dihydrogen phosphate.

Comparative Study of Pure and Magnesium Doped Cadmium Mercury Thiocyanate Single Crystals – Gel Technique

Growth of magnesium doped cadmium mercury thiocyanate single crystals from silica gel by the process of diffusion and a comparative study with pure cadmium mercury thiocyanate are discussed. The X-ray diffraction studies reveal the crystal lattice of the doped crystal to be tetragonal showing that the incorporation of the metallic dopant has not altered the structure of the parent crystal. Investigation on the crystalline perfection of the grown crystal by high resolution X-ray diffraction analysis reveals the quality of the doped crystal to be extremely good. Fourier transform infrared and transmission spectra were also recorded for the grown crystals. The thermal stabilities of the crystals were investigated by thermogravimetric and differential thermal analyses. Vickers microhardness studies reveal that the presence of dopant has changed the nature of the crystal from soft to hard material category. The second harmonic generation efficiencies of the crystals were measured with respect to urea.

Synthesis, spectroscopic and structural investigation of Zn(NCS) 2(nicotinamide) 2 and [Hg(SCN) 2(nicotinamide)] n

Zinc(II) and mercury(II) thiocyanate complexes with nicotinamide, bis(nicotinamide- N)-bis(thiocyanato- N)zinc(II) ( 1) and catena-[nicotinamide- N-( μ-thiocyanato- S, N)(thiocyanato- S)mercury(II)] ( 2), have been prepared and characterized by spectroscopic, thermal and X-ray crystallographic methods. The vibrational bands of diagnostic value are compared to the values of the free ligand and the data are in good correlation with the X-ray results. Centrosymmetrical hydrogen bonded dimers are found, R 2 2(10) in 1 and R 2 2(8) in 2.

Construction and evaluation of a flow injection micro-analyser based on urethane–acrylate resin

A flow injection micro-analyser with an integrated injection device and photometric detection is described. Channels measuring 205–295 μm depth by 265–290 μm maximum width were manufactured by deep UV lithography on two layers of urethane–acrylate oligomers-based photoresist. Hypodermic syringe needles (450 μm diameter) were connected to the channels for introduction of solutions into the system. Plastic optical fibres were connected to the ends of a 5.0 mm long channel, in order to conduct the light from and to a homemade photometer. The device has a total volume of 7.0 μL and three different sample volumes (0.09, 0.22 and 0.30 μL) can be inserted into the system by choosing the appropriate loop of the hydrodynamic injection approach. The micro-analyser, designed as a single line manifold, was evaluated by determining chloride in waters (mercuric thiocyanate method), and chromium (VI) in wastewater and total chromium in metallic alloys (diphenylcarbazide method). For chloride determination two micro-pumps were employed to impel the solutions, while for chromium determination this task was performed by a conventional peristaltic pump. The results obtained in all determinations did not differ significantly from the reference methods at a confidence level of 95%. In the chloride determination, a flow rate of 50 μL min −1 was used, providing a sample frequency of 45 injection h −1, generating ca. 0.7 mg of Hg(II) after an 8-h working day (ca. 20 mL of solution). This result suggests the potential of the micro-analyser towards the reduction of waste, following the philosophy of Green Chemistry.

Vickers microhardness studies on cadmium mercury thiocyanate (CMTC) single crystals grown in silica gel

Vickers microhardness study was carried out on the (110) face of the gel-grown cadmium mercury thiocyanate (CMTC) single crystal, subjected to the loads 10, 25 and 50 g. The measurements were made at room temperature with the indentation time as 10 s. Vickers hardness number Hv was calculated and it is found to increase with the applied load. Mayer's index number ‘ n’ and elastic stiffness constant were calculated. The anisotropy of the crystal is also studied. The results are discussed in detail.

Argentimetric assay of ranitidine in bulk drug and in dosage forms

Two simple, rapid and cost-effective methods based on titrimetric and spectrophotometrictechniques are described for the assay of RNH in bulk drug and in dosage forms using silver nitrate, mer-cury(II)thiocyanate and iron(III)nitrate as reagents. In titrimetry, an aqueous solution of RNH is treatedwith measured excess of silver nitrate in HNO 3 medium, followed by determination of unreacted silvernitrate by Volhard method using iron(III) alum indicator. Spectrophotometric method involve the addi-tion a known excess of mercury(II)thiocyanate and iron(III)nitrate to RNH, followed by the measurementof the absorbance of iron(III)thiocyante complex at 470 nm. Titrimetric method is applicable over 4-30mg range and the reaction stoichiometry is found to be 1:1 (RNH: AgNO 3 ). In the spectrophotometricmethod, the absorbance is found to increase linearly with concentration of RNH which is corroboratedby the correlation coefficient of 0.9959. The system obey Beer’s law for 5-70 μg mL -1 . The calculatedapparent molar absorptivity and sandell sensitivity values are found to be 3.27 × 10 3 L mol -1 cm -1 , 0.107μg cm -2 respectively.

Mercury thiocyanate coordination polymers generated from rigid or flexible organic nitrogen donor-based ligands

Four mercury(II) thiocyanate–organic polymeric complexes, [Hg(μ-4,4-bipy)(SCN)2]n (1), [Hg(μ-bpa)(SCN)2]n (2), [Hg(μ-bpe)(SCN)2]n (3), [Hg(μ-bpp)(SCN)2]n (4) {4,4-bipy=4,4′-bipyridine, bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethene and bpp=1,3-di(4-pyridyl)propane} were prepared from reactions of mercury(II) thiocyanate with four rigid and flexible organic nitrogen donor-based ligands under thermal gradient conditions, brunched tube method. All these compounds were structurally determined by X-ray single-crystal diffraction. The thermal stabilities of compounds 1–4 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Solid state luminescent spectra of compounds 1 and 3 indicate intense fluorescent emissions at 430 and 468nm, respectively.

Study of optimum growth condition and characterization of zinc mercury thiocyanate (ZMTC) single crystals in silica gel

Some bimetallic thiocyanate complexes exhibit excellent nonlinear optical properties. Single crystals of one such material, zinc mercury thiocyanate ZnHg(SCN) 4 have been grown in silica gel with gel technique by the process of diffusions and the optimum growth condition has been studied. Crystals of 4 mm length have been obtained. Their structural, optical and thermal properties have been studied. Structural analysis was carried out using an X-ray diffractometer and the crystal structure was confirmed to be tetragonal. Fourier transform infrared spectrum was obtained to confirm the functional groups. Transmission spectrum has been recorded in the solution state and the cut-off wavelength has been determined. Thermal stability of the grown crystal has been investigated by thermogravimetric and differential thermal analyses. Nonlinear optical property of the crystal has been confirmed using the Kurtz powder technique and a study of its second harmonic generation efficiency in comparison with urea has been made.