Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

 

 

 

VOLUME 52A

NUMBER 1

JANUARY 2013

 

CONTENTS

 

 

9

 

Solvent effect on the photophysical behavior of some bischromophoric dyes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sasmita Baliarsingh, Sabita Patel & Bijay K Mishra*

 

 

 

Hemicyanine dyes experience reversal in solvatochromism delineating a polarity switch for solvents at ET(30) value of 52-55.

 

 

 

 

 

 

19

 

Intermolecular interaction in the benzene-Arn and benzene dimer van der Waals complexes: DFT analysis of the charge distribution and electric response properties

 

 

 

 

 

 

 

 

 

 

 

 

 

Rifaat Hilal*, Walid M I Hassan, Abdulrahman Alyoubi, Saadallah G Aziz & Shabaan A K Elroby

 

 

 

The wB97-XD method reproduces the well positions and well depths of the bz-Ar and bz-bz clusters to a high degree of accuracy with the experimental data.

 

 

 

 

28

 

Selective hydrogenation of crotonaldehyde over supported Ir catalysts: Effect of surface acidity on catalyst deactivation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Xiao Hong, Ji-qing Lu, Bo Li, Ling-yun Jin,
Geng-shen Hu, Yue-juan Wang* & Meng-fei Luo
*

 

 

 

Ir/TiO2 catalyst shows the highest initial conversion of crotonaldehyde, while the Ir/SnO2 catalyst shows the lowest activity. Deactivation of Ir catalysts strongly depends on the surface acidity.

 

 

 

 

Notes

 

34

 

Syntheses, structures and properties of pentacoordinated zinc(II) halide complexes containing a tridentate Schiff base as end capping ligand

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Subhasis Roy, Subhasish Kundu, Kishalay Bhar, Smita Satapathi, Partha Mitra &
Barindra Kumar Ghosh
*

 

 

 

Pentacoordinated zinc(II) halide complexes in combination with a tridentate Schiff base show chelation behavior of Schiff base and terminal motif of halides. Intermolecular C-HO, C-HBr and C-HI hydrogen bonds along with pp and C-Hp interactions indicate different crystalline aggregates. The complexes display intraligand 1(p-p*) fluorescence in DMF solutions at room temperature.

 

 

 

 

41

 

Bis-phosphine palladium(II) mesityl chalcogenolate complexes: Synthesis and structure of [Pd(SeMes)2(dppe)]

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rohit Singh Chauhan, G Kedarnath,
James A Golen, Arnold L Rheingold & Vimal K Jain*

 

 

 

Reactions of [PdCl2(PP)] (PP = dppe, dppp) with Pb(SMes)2 or NaEMes yield mononuclear complexes of the type, [Pd(EMes)2(PP)] (Mes = mesityl (2,4,6-Me3C6H2); E = S, Se or Te) while the reaction of [PdCl2(dppp)] with NaTeMes affords a trinuclear complex, [Pd3(-Te)2(dppp)3]2+.

 

 

 

 

45

 

Synthesis and characterization of nickel(II) complex of p-[N, N-bis (2-chloroethyl)amino]benzaldehyde-4-ethyl thiosemicarbazone

 

 

 

 

 

 

 

 

 

S Anitha , J Karthikeyan* & A Nityananda Shetty

 

 

 

 Image generated by GPL Ghostscript (device=pnmraw)

 

 

 

51

 

A facile synthetic route to flower-like NiO and its catalytic properties

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Dishan Zhou, Aifeng Yan, Ying Wu* & Tinghua Wu*

 

 

 

Flower-like NiO synthesized via a facile synthetic route exhibits better catalytic performance for oxidative dehydrogenation of ethane reaction as compared to conventional particulate NiO.

 

 

 

 

57

 

Photocatalytic and antibacterial activities of CdS nanoparticles prepared by solvothermal method

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Zhihong Jing*, Lihua Tan, Fen Li, Jun Wang,
Yucai Fu
& Qian Li

 

 

 

 

 

 

63

 

Photocatalytic destruction of an organic dye,
Acid Red 73 in aqueous ZnO suspension using UV light energy

 

 

 

 

 

 

 

 

 

 

 

 

 

A Nilamadanthai, N Sobana , B Subash,
M Swaminathan & M Shanthi
*

 

 

 

 

 

 

 

69

 

Guide to Authors

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 9-18

 

 

Solvent effect on the photophysical behavior of some bischromophoric dyes

 

Sasmita Baliarsingha, Sabita Patelb & Bijay K Mishraa, *

aCentre of Studies in Surface Science and Technology, School of Chemistry, Sambalpur University,
Jyoti Vihar, Burla 768 019, India

bDepartment of Chemistry, National Institute of Technology, Rourkela 769 008, India
Email: bijaym@hotmail.com

Received 18 September 2012; revised and accepted 24 December 2012

Absorption and emission spectra of some bischromophoric dyes, having 4-(p-N,N-dimethylaminostyryl) pyridinium units flanked by spacers with 2, 3, 4 and 6 methylene units, in different organic solvents have been subjected to multiple regression analysis with twelve different solvent parameters. Optimization of multiparametric regression models has been achieved by successive exclusion of variable technique. The validity of the regression models has been established from the linearity of the calculated and observed transition energy relating to absorption spectra and Stokes shift. Variation in the trends in change of photophysical behavior of the dyes results in classification of the solvents into two distinct classes, viz., hydroxylic and dipolar aprotic solvents. A higher dipole moment of the excited state than of the ground state of all these dyes has been deduced from the Stokes shift. The study on quantitative Stokes shift-solvent parameter relationship reveals a significant change in the behavior of dyes with two methylene units as compared to the other dyes. To this effect different types of hydrogen bonding has been proposed.

Keywords: Photophysical behavior, Solvent effect, Solvatochromism, Polarity switch, Absorption spectra, Emission spectra, Solvent parameters, Stokes shift, Hemicyanine dyes, Bischromophoric dyes, Successive exclusion of variable

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 19-27

 

 

Intermolecular interaction in the benzene-Arn and benzene dimer van der Waals complexes: DFT analysis of the charge distribution and electric response properties

Rifaat Hilala, b, *, Walid M I Hassanb, Abdulrahman Alyoubia, Saadullah G Aziza & Shabaan A K Elrobya, c

aChemistry Department, Faculty of Science, King Abdulaziz University, B.O. 80203, Jeddah 21589, Saudi Arabia

bChemistry Department, Faculty of Science, Cairo University, Giza, Egypt

Email: rhilal@kau.edu.sa

cChemistry Department, Faculty of Science, Beni-suief University, Beni-suief, Egypt

Received 10 June 2012; revised and accepted 18 December 2012

The performance of the DFT/B-97-D and wB97-D methods to reproduce the isotropic non-bonded interaction and the electric response properties in the benzeneargon and the π-π interaction in the benzene dimer have been studied. The PES for the interaction of benzene and argon with all possible Arn-benzene (n = 1, 2) conformations has been explored. Results indicate that the wB97-XD method is capable of reproducing well positions and depths for the studied benzene-Ar and benzene-benzene clusters to a high degree of accuracy and compare well with the experimental and best benchmark calculations. Satisfactory results have also been obtained for the benzene-X (X = He, Ne and Kr) clusters. The features of the charge density distributions of the studied benzene-Ar van der Waal complexes have been analyzed by calculating the dipole and higher multipole moments and the static polarizibility, its anistropic part and the interaction polarizibility. Trends and relationships to the dispersion interaction energy are suggested. Natural bond orbital analyses of the benzene-Arn vdw complexes show clearly that all carbon valence orbitals are over-populated by about 21% at the expense of the hydrogen atoms valence orbitals. These data also indicate that argon behaves as electron donor in the Ar-benzene vdw complex, and hence, the slight positive charge on argon is at on the expense of its valence (non-bonding) p-orbitals.

Keywords: Theoretical chemistry, Density functional calculations, Ab initio calculations, Dispersion interactions,
van der Waals clusters, Benzene-argon clusters, Benzene-benzene clusters

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 28-33

 

 

Selective hydrogenation of crotonaldehyde over supported Ir catalysts:
Effect of surface acidity on catalyst deactivation

Xiao Hong, Ji-qing Lu, Bo Li, Ling-yun Jin, Geng-shen Hu, Yue-juan Wang* & Meng-fei Luo*

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry,
Zhejiang Normal University, Jinhua 321004, China

Email: znuwyj@zjnu.cn (YJW)/ mengfeiluo@zjnu.cn (MFL)

Received 9 July 2012; revised and accepted 17 December 2012

Ir catalysts supported on various oxides (TiO2, ZrO2, CeO2, SnO2, and La2O3) have been prepared by an impregnation method and applied for selective hydrogenation of crotonaldehyde. It is found that the catalytic behavior strongly depends on the surface acidity of the catalysts. The highest activity and selectivity are obtained on the Ir/TiO2 catalyst, with a crotonaldehyde conversion of 43.2% and a selectivity to crotyl alcohol of 80.9% at
80 oC. Also, all the catalysts are deactivated during the reaction due to polymeriation of crotonaldehyde molecules on the surface of the catalysts, as evidenced by FTIR data and temperature-programmed oxidation of the spent catalysts. It is also found that the deactivation rates are related to the amount of surface acid sites on the catalysts. The Ir/CeO2 catalyst with the highest amount of surface acid sites is deactivated more rapidly than the Ir/La2O3 catalyst with the lowest amount of surface acid sites.

Keywords: Catalysts, Supported catalyst, Iridium, Hydrogenation, Selective hydrogenation,
Impregnation method,Oxides, Aldehydes, Unsaturated aldehydes, Alcohols, Crotonaldehyde,
Crotyl alcohol

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 34-40

 

 

Syntheses, structures and properties of pentacoordinated zinc(II) halide complexes containing a tridentate Schiff base as end capping ligand

Subhasis Roya, Subhasish Kundua, Kishalay Bhara, Smita Satapathia,
Partha Mitrab & Barindra Kumar Ghosha, *

aDepartment of Chemistry, The University of Burdwan, Burdwan 713 104, India

Email: barin_1@yahoo.co.uk

bDepartment of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India

Received 10 September 2012; revised and accepted 13 December 2012

Three neutral pentacoordinated complexes of the type [Zn(L)X2].nH2O [L = (N,N-diethyl,N'-(pyridin-2-yl)benzylidene)-ethane-1,2-diamine; X = Cl-, n = 0.5, X = Br-, n = 0 and X = I-, n = 0] have been isolated using 1:1 molar ratio of the corresponding zinc(II) halide and the tridentate Schiff base. The compounds are characterized by elemental analyses, spectroscopic and other physicochemical data. Single crystal X-ray structural analyses reveals that the zinc(II) center in these complexes adopts a distorted square pyramidal geometry with a ZnN3X2 chromophore. Intermolecular
C-HO, C-HBr and C-HI hydrogen bonds along with
pp and C-Hp interactions indicate different crystalline aggregates. The complexes display intraligand 1(p-p*) fluorescence in DMF solutions at room temperature.

Keywords: Coordination chemistry, Zinc, Schiff bases, Tridentate Schiff bases, Crystal structures, Luminescence,
End capping ligands

Indian Journal of Chemistry

Vol 52A, January 2013, pp. 41-44

 

 

Bis-phosphine palladium(II) mesityl chalcogenolate complexes: Synthesis and structure of [Pd(SeMes)2(dppe)]

 

Rohit Singh Chauhana, G Kedarnatha, James A Golenb, Arnold L Rheingoldb & Vimal K Jaina, *

aChemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India

Email: jainvk@barc.gov.in

 

bDepartment of Chemistry and Biochemistry, University of California, San Diego,
La Jolla, California 92093-0358, USA

Email: arheingold@ucsd.edu

Received 4 September 2012; accepted 21 December 2012

 

Reactions of [PdCl2(PP)] (PP = dppe, dppp) with Pb(SMes)2 or NaEMes yield mononuclear complexes of the type, [Pd(EMes)2(PP)] (Mes = mesityl (2,4,6-Me3C6H2); E = S, Se or Te). However, in the reaction of [PdCl2(dppp)] with NaTeMes, a trinuclear complex, [Pd3(-Te)2(dppp)3]2+ is formed via Te-C bond cleavage in CH2Cl2. These complexes have been characterized by elemental analyses and NMR (1H, 31P{1H}) spectroscopy. The molecular structure of [Pd(SeMes)2(dppe)] has been established by single crystal X-ray diffraction analysis.

Keywords: Coordination chemistry, Palladium, Bis-phosphines, Organochalcogenolates, Chalcogenolates,
X-ray structure

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 45-50

 

 

Synthesis and characterization of nickel(II) complex of p-[N, N-bis-
(2-chloroethyl)amino]benzaldehyde-4-ethyl thiosemicarbazone

S Anithaa, J Karthikeyana, * & A Nityananda Shettyb

aDepartment of Chemistry, Sathyabama University,
Chennai 600 119, India

Email: dr.j.karthikeyan@gmail.com; jkarthik_chem@rediffmail.com

bDepartment of Chemistry, National Institute of Technology Karnataka, Mangalore 575 025, India

Received 23 July 2012; revised and accepted 11 December 2012

New square planar complex of Ni(II) (S = 0) with p-[N, N-bis (2-chloroethyl)aminobenzaldehyde-4-ethyl thiosemicarbazone has been synthesized and characterized by elemental analysis, IR, electronic, 1H-NMR spectroscopy. The crystal structures of the free thiosemicarbazone and complex have been determined by single crystal X-ray diffraction technique. In the complex, the thiosemicarbazone is coordinated to nickel through square planar (1: 2 complex) SNNS mode. The complex crystallizes in the monoclinic space group C2/c. The complex has been tested for their antibacterial activity against various pathogenic bacteria. From this study, it was found out that the activity of complex is comparable with that of the conventional bacteriocide Streptomycin compared to free thiosemicarbazone.

Keywords: Coordination chemistry, Thiosemicarbazones, SNNS donor type complex, Nickel

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 51-56

 

 

A facile synthetic route to flower-like NiO and its catalytic properties

Dishan Zhou, Aifeng Yan, Ying Wu* & Tinghua Wu*

Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry,
Zhejiang Normal University, Jinhua 321004, Zhejiang, China

Email: yingwu@zjnu.cn (YW)/ thwu@zjnu.cn (TW)

Received 28 September 2012; revised and accepted 18 December 2012

NiO with flower-like morphology has been synthesized via the simple homogeneous precipitation method by using nickel nitrate and urea at 115 C for 1.5 h. The physicochemical properties of as-obtained NiO are characterized by X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, N2 sorption, and H2 temperature-programmed reduction. The results show that the flower-like NiO exhibits a larger surface area, higher reducibility and better catalytic activity for oxidative dehydrogenation of ethane to ethylene, compared to conventional particulate NiO.

Keywords: Nickel oxide, Precipitation, Homogeneous precipitation, Flower-like morphology, Dehydrogenation, Oxidative dehydrogenation, Ethane dehydrogenation, Ethylene

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 57-62

 

 

Photocatalytic and antibacterial activities of CdS nanoparticles

prepared by solvothermal method

 

Zhihong Jinga, b *, Lihua Tana, Fen Lia, Jun Wanga, Yucai Fua & Qian Lia

aCollege of Chemistry and Chemical Engineering Qufu Normal University, Qufu Shandong 273165, PR China

Email: zhhjing@126.com

 

bKey Laboratory of Colloid and Interface Chemistry Shandong University, Ministry of Education, Jinan 250100,
PR
China

 

Received 4 September 2012; revised and accepted 24 December 2012

 

CdS nanoparticles have been prepared via solvothermal method, by reaction of cadmium chloride and thiourea in ethylenediamine and ethanol mixed solvent. The characteristics of the CdS nanoparticles have been studied by XRD, TEM, HRTEM and FT-IR. The photoluminescence spectra of the CdS nanoparticles in three organic solvents, viz., ethanol, tetrahydrofuran and N-N-dimethyl formamide, have been conducted. The photocatalytic properties of the CdS nanoparticles have been evaluated for the degradation of five different dyes under irradiation of UV light. In addition, the antibacterial activitiy of the CdS nanoparticles against Escherichia coli have been investigated for the first time by microcalorimetric method. The results indicate that the as-prepared CdS nanoparticles can be used as not only a high-powered photocatalyst for potential application in the fields of industrial and environmental control but also as an excellent antibacterial agent.

Keywords: Cadmium sulphide, Nanoparticles, Solvothermal method, Photocatalytic activity, Antibacterial activity,
Microcalorimetry methods

 

 

 

 

 

Indian Journal of Chemistry

Vol. 52A, January 2013, pp. 63-67

 

 

Photocatalytic destruction of an organic dye, Acid Red 73 in aqueous ZnO suspension using UV light energy

A Nilamadanthai, N Sobana, B Subash, M Swaminathan & M Shanthi*

Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu, India

Email: shanthimsm@gmail.com

 

Received 23 May 2012; revised and accepted 21 December 2012

Photocatalytic degradation of the azo dye Acid Red 73 (AR 73) in aqueous solution with zinc oxide as photocatalyst in slurry form has been investigated using UV light. There is a significant difference in adsorption of dye on ZnO surface with the change in solution pH. The effects of various parameters such as catalyst loading, pH and initial concentration of the dye on degradation have been determined. The degradation is strongly enhanced in the presence of electron acceptors such as H2O2, (NH4)2S2O8 and KBrO3. Addition of dye-assisting chemicals such as Na2CO3 and NaCl inhibits the removal rate. The photodegradation analysis has been carried out using Langmuir-Hinshelwood kinetic model.

Keywords: Photocatalytic degradation, Degradation, UV light, Acid Red 73, Dye degradation, Zinc oxide, Oxides