• A Shunmugasundaram

      Articles written in Journal of Chemical Sciences

    • Correlation of ground and excited state dissociation constants oftrans-para- and ortho-substituted cinnamic acids

      R Murugesan B Rajasekar T Lekshmana Thanulingam A Shunmugasundaram

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      The ground and excited state dissociation constants oftrans- para- and ortho-substituted cinnamic acids have been determined in 50% (v/v) dioxan-water mixture at 30°C using the Forster cycle. The measured dissociation constants are analysed in the light of single and dual substituent parameter (DSP) equations. Excited state dissociation constants ofp-substituted cinnamic acids correlate well with the exalted substituent constants. The DSP method of analysis shows that resonance effect is predominant relative to inductive effect in the excited state than in the ground state for the para-substituted acids. The single parameter equation gives poor correlation for the ortho-substituted acids. However, the DSP analysis shows fairly good correlation. The inductive effect is predominant relative to the resonance effect in the excited state than in the ground state

    • Spectral and voltammetric studies on titanium substituted Keggin-type heteropolyanions

      R Murugesan P Sami T Jeyabalan A Shunmugasundaram

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      Bonding and redox properties of mono- and dititanium substituted 12-heteropolytungsto-phosphates and their complexes with bivalent Mn, Co, Ni and Cu are studied by UV-Vis, ESR and cyclicvoltammetric techniques. The heteropoly blue analogue [TiIIITiIVW10PO40]8− is unstable and its presence in solution is proved by optical and ESR spectroscopy. ESR results reveal that the odd electron is trapped on the titanium atom at 77 K. The optical electronegativity of Ti(III) in this heteropoly blue is estimated to be 2.4 from the intervalence charge transfer (IVCT) bands. X-ray powder diffraction results show that the complexes K5MII[Ti2W10PO40].xH2O(MII = Cu or Mn) are isomorphous with K7[Ti2W10PO40].6H2O. Electronic spectroscopy indicates very high symmetry around the bivalent metal ion M in the K5MII[Ti2W10PO40].xH2O complexes. This high symmetry is confirmed in K5Cu[Ti2W10PO40] by the observation of dynamic Jahn-Teller (JT) distortion at 300 K and static JT distortion at 77 K.

    • EPR investigations of electron transfer in one-electron reduced α-1,4 K5[PV2W10O40].3H2O

      C M Varghese A Shunmugasundaram R Murugesan T Jey Abalan

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      Heteropoly blues of α-1,2 and α-1,4 isomers of [PV2W10O40]5−have been prepared by using the electrochemical technique. EPR spectra, measured as a function of temperature over a wide range (20-300 K), are explicable in terms of electron-hopping processes in heteropoly blues. Temperature dependence of A∥of the isomers suggest that the activation energy for electron hopping is greater for the α-1,4 isomer than the α-1,2 isomer. Other parameters like stability of the blues and intra-molecular electron transfer rate constants are also evaluated using EPR as the tool.

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