Subbiah Meenakshisundaram

Enhancement of crystalline perfection by organic dopants in ZTS, ADP and KHP crystals as investigated by high-resolution XRD and SEM

To reveal the influence of complexing agents on crystalline perfection, tristhiourea zinc(II) sulfate (ZTS), ammonium dihydrogen phosphate (ADP) and potassium hydrogen phthalate (KHP) crystals grown by slow-evaporation solution growth technique using low concentrations (5 x 10 -3 M) of dopants like ethylenediamminetetraacetic acid (EDTA) and 1,10-phenanthroline (phen) were characterized by high-resolution X-ray diffractometry (XRD) and scanning electron microscopy (SEM). High-resolution diffraction curves (DCs) recorded for ZTS and ADP crystals doped with EDTA show that the specimen contains an epilayer, as observed by the additional peak in the DC, whereas undoped specimens do not have such additional peaks. On etching the surface layer, the additional peak due to the epilayer disappears and a very sharp DC is obtained, with full width at half-maximum (FWHM) of less than 10 arcsec, as expected from the plane wave dynamical theory of X-ray diffraction for an ideally perfect crystal. SEM micrographs also confirm the existence of an epilayer in doped specimens. The ZTS specimen has a layer with a rough surface morphology, having randomly oriented needles, whereas the ADP specimen contains a layer with dendric structure. In contrast to ADP and ZTS crystals, the DC of phen-doped KHP shows no additional peak, but it is quite broad (FWHM = 28 arcsec) with a high value of integrated intensity, p (area under the DC). The broadness of the DC and the high value of p indicate the formation of a mosaic layer on the surface of the crystal. However, similar to ADP and ZTS, the DC recorded after etching the surface layer of the KHP specimen shows a very sharp peak with an FWHM of 8 arcsec. An SEM photograph of phen-doped KHP shows deep cracks on the surface, confirming the mosaicity. After removing the surface layer, the SEM pictures reveal a smooth surface. A similar trend is observed with other complexing agents, like oxalic acid, bipy and picolinic acid. However, only typical examples are described in the present article where the effects were observed prominently. The investigations on ZTS, ADP and KHP crystals, employing high-resolution XRD and SEM studies, revealed that some organic dopants added to the solution during the growth lead to the formation of a surface layer, due to complexation of these dopants with the trace metal ion impurities present in the solution, which prevents the entry of impurities, including the solvent, into the crystal, thereby assisting crystal growth with high crystalline perfection. The influence of organic dopants on the second harmonic generation efficiency is also investigated.

Rare earth cerium doping effects in nonlinear optical materials: potassium hydrogen phthalate (KHP) and tris(thiourea)zinc(II) sulfate (ZTS)

The influence of Ce(IV) doping on ZTS and KHP crystals over a concentration range from 1 to 10 mol% in the solution during crystallization, which leads to a true concentration range from few ppm to few tens of ppm in the crystals has been investigated. The XRD and FT-IR analyses indicate that the crystal undergoes considerable stress as a result of doping. Incorporation of the Ce(IV) dopant into the crystal lattice was well confirmed by energy dispersive X-ray spectroscopy (EDS) and quantified by inductively coupled plasma (ICP) technique. The high-resolution X-ray diffraction (HRXRD) studies reveal that Ce doping in KHP leads to degradation of crystal quality whereas ZTS can accommodate Ce predominantly at the substitutional sites without any degradation of crystalline perfection. The second harmonic generation (SHG) efficiency is not influenced by Ce doping in the KHP crystals while in ZTS crystals, it is enhanced to a considerable extent correlated with moderately improved crystalline perfection.

Optical, vibrational, NBO, first-order molecular hyperpolarizability and Hirshfeld surface analysis of a nonlinear optical chalcone.

The synthesis of (1E,4E)-1,5-di-p-tolylpenta-1,4-dien-3-one (DTDO) was done and its single crystals were grown by slow evaporation solution technique from 4-methylbenzaldehyde, acetone solution at room temperature. Crystal structure is determined by single crystal X-ray diffraction analysis and reveals that it belongs to the monoclinic system with four molecules in the unit cell (space group C2). The emission of green light from the sample confirms the second harmonic generation (SHG) of the specimen responsible for nonlinear optical property. The various vibration patterns of the specimen have been investigated by Fourier transform infrared and Fourier transform Raman spectroscopy. Optimized molecular geometry, vibrational patterns of DTDO are derived from density functional theory (DFT) calculations and the results are compared with experimental one. The molecular stability and bond strengths were investigated by applying the natural bond orbital analysis. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron density with molecular electrostatic potential (MEP). Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gaps were calculated. The other molecular properties like charge transfer are explained using Mulliken population analysis and the first-order molecular hyperpolarizability (β) of the specimen is also estimated and SHG efficiency of DTDO was found to be 3.9 times that of KDP. Fingerprint plots and Hirshfeld surfaces were used to locate and analyze the molecular surface and bonding interactions in various methodologies utilized in the establishment of the relative energies.

1,10-Phenanthroline catalysed HCrO4- oxidation of some substituted trans-cinnamic acids

Catalytic activity of 1,10-phenanthroline(Phen) in the HCrO4− oxidation of substituted trans-cinnamic acids to the corresponding benzaldehydes, has been investigated in acidic medium. The CrVI–Phen complex is believed to be the probable electrophile in the catalysed oxidation. The catalytic activity is quite likely to be due to the shift in redox potential of the oxidant. Pyridine has no effect in this conversion. The catalytic efficiencies of pyridine bases are compared. Nonadherence to LFER studies, resulting in a continuously changing Hammett curve, gives an insight into the nature of the transition state.

Os(VIII) -catalysed oxidation of sulfides by sodium salt of N-chlorobenzenesulfonamide

Abstract Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N -chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH∼8.7) t -butanol–water (1:1 v/v) medium. Significant retarding influence of [OH − ] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO 2 substituents.

Growth and characterization of Fe3+-doped bis(thiourea)zinc(II) chloride crystals.

Fe3+-doping at ∼10 mol% in aqueous medium during crystal growth by slow evaporation solution method in bis(thiourea)zinc(II) chloride (BTZC) leads to form a new compound C2H8Cl2N4S2Zn0.93Fe0.07 (BTZCF) which crystallizes in orthorhombic structure with centrosymmetric space group Pnma though the parent compound BTZC crystallizes in noncentrosymmetric structure with space group Pn2(1)a. The interesting feature observed in this new crystal is that though it crystallizes in centrosymmetric structure, it exhibits positive SHG result (weak signal), quite likely due to possible surface effects or internal stress. The calculated first-order hyperpolarizability is 1.457×10(-30) esu which is ∼5.5 times that of urea. Fe3+-doping enhances the transmittance to a significant extent. Comparison of the thermal analysis results by DSC reveals the incorporation of dopant into the crystalline matrix. The high resolution XRD studies reveal that the crystalline quality is improved considerably when the doping level is reached to ∼10 mol%.

Crystal growth, characterization and theoretical studies of 4-aminopyridinium picrate.

Single crystals of 4-aminopyridinium picrate (APP) were grown by slow evaporation of a mixed solvent system methanol-acetone (1:1, v/v) containing equimolar quantities of 4-aminopyridine and picric acid. Structure is elucidated by single crystal XRD analysis and the crystal belongs to monoclinic system with four molecules in the unit cell (space group P21/c) and the cell parameter values are, a=8.513 Å (±0.015), b=11.33 Å (±0.02), c=14.33 Å (±0.03) and β=104.15° (±0.019), V=1340 A(3) (±6) with refined R factors R1=0.0053 and wR2=0.0126. The electron density mapping is interpreted to find coordinates for each atom in the crystallized molecules. The various functional groups present in the molecule are confirmed by FT-IR analysis. UV-visible spectral analysis was used to determine the band gap energy of 4-aminopyridinium picrate. Powder X-ray diffraction pattern reveals the crystallinity of the as-grown crystal and it closely resembles the simulated XRD from the single crystal XRD analysis. Scanning electron microscopy reveals the surface morphology of the grown crystal. Optimized geometry is derived by Hartree-Fock theory calculations and the first-order molecular hyperpolarizability (β), theoretically calculated bond length, bond angles and excited state energy from theoretical UV-vis spectrum were estimated.

Synthesis, crystal growth, characterization and theoretical studies of 4-aminobenzophenonium picrate.

Single crystals of 4-aminobenzophenonium picrate (4ABPP) were grown by slow evaporation of a mixed solvent system methanol-acetone (1:1,v/v) containing equimolar quantities of picric acid and 4-aminobenzophenone. The proton and carbon signals are confirmed by nuclear magnetic resonance spectroscopy. The various functional groups present in the molecule are identified by FT-IR analysis. Optimized geometry, first-order molecular hyperpolarizability (β), polarizability (α), bond length, bond angles and excited state energy from theoretical UV were derived by Hartree-Fock calculations. The complete assignment of the vibrational modes for 4-aminobenzophenonium picrate was performed by the scaled quantum mechanics force field (SQMFF) methodology using potential energy distribution. Natural bond orbital (NBO) calculations were employed to study the stabilities arising from charge delocalization and intermolecular interactions of 4ABPP. The atomic charge distributions of the various atoms present in 4ABPP are obtained by Mulliken charge population analysis. The as-grown crystal is further characterized by thermal and optical absorbance studies.

Synthesis, structure, growth and characterization of an organic crystal: 1,5-diphenylpenta-2,4-dien-1-one

1,5-Diphenylpenta-2,4-dien-1-one (DDO) chalcone single crystals, synthesized by a base-catalysed aldol condensation reaction between cinnamaldehyde and acetophenone, have been grown by the slow evaporation of an ethanol solution. The crystals belong to the orthorhombic system with centrosymmetric space group Pbca. The DDO crystals are transparent in the visible region and have a lower optical cut-off at ∼445 nm with a band-gap energy of 2.87 eV. Thermogravimetry/differential scanning calorimetry thermal analysis shows that the crystal is stable up to 375 K and it has a good chemical stability. The vibrational patterns of the chalcone have been investigated by Fourier transform IR and Fourier transform Raman spectroscopy. Microhardness studies were also carried out to elucidate the mechanical behaviour. Theoretical calculations were performed using the Hartree–Fock method with 6-31G(d,p) as the basis set, and the first-order hyperpolarizability is 7.077 × 10−30 electrostatic units, which is >25 times that of urea. The crystalline perfection evaluated by high-resolution X-ray diffraction analysis reveals multiple peaks. The molecular packing leads to a centrosymmetric arrangement, resulting in zero second harmonic generation [χ(2) = 0] efficiency. Interestingly, the bromo- and chloro-substituted chalcones are good nonlinear optical materials.

Effect of alkaline earth and transition metals doping on the properties and crystalline perfection of potassium hydrogen phthalate (KHP) crystals

The influence of alkaline earth metal (Mg) and transition metal (Hg) doping on the properties and crystalline perfection of potassium hydrogen phthalate (KHP) crystals has been described. Incorporation of dopant into the crystalline matrix even at the low concentrations was well confirmed by energy dispersive X-ray spectroscopy (EDS). Further, high-resolution X-ray diffraction (HRXRD) studies indicate predominant substitutional site occupancy for Mg. Heavy doping results in internal structural grain boundaries due to stress aroused in the lattice caused by the entry of dopants into the crystalline matrix. The transition metal (Hg) doping results in multi-peaks in the diffraction curve (DC) with a wide angular spread and the site occupancy seems to be predominantly interstitial positions in the crystal lattice, quite likely due to its bigger size in comparison with alkaline earth metal. The reduction in the intensity observed in powder X-ray diffraction (XRD) for both types of doped specimens and slight shifts in vibrational frequencies reveal minor structural variations. It is observed that the doping with high concentrations of metal facilitates nonlinearity and enhances the second harmonic generation (SHG) efficiency to a significant extent.