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Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR,optical and magnetic susceptibility measurements
Authors:TAPAN KUMAR KUNDU  PERIAKARUPPAN T. MANOHARAN
Affiliation:Regional Sophisticated Instrumentation Centre and the Department of Chemistry , Indian Institute of Technology Madras , Chennai, 600 036, India
Abstract:Single-crystal variable temperature EPR, optical and polycrystalline magnetic susceptibility studies have been made on a novel six-coordinate Ag(II) complex. Temperature dependent EPR studies on pure single crystals of this compound reveal that dynamic Jahn-Teller distortion operates above 230 K, between 230 K and 120K static Jahn-Teller distortion sets in and below 110 K there is evidence of exchange interaction. Crystal g values were obtained by least-squares fitting with the data obtained from the orientation dependent EPR spectra of the undiluted single crystal of this complex at 300 K and 77 K. From an optical study the Jahn-Teller stabilization energy is found to be ~2250cm?1. Comparison of Absmax values for other silver(II) compounds enables us to conclude that the formal geometry of this complex is a tetragonally distorted octahedral. Infrared spectra of this complex were also recorded over a wide range of temperature. Magnetic susceptibility measurements over a wide range of temperature on the powder sample of this compound reveal that the complex is antiferromagnetically coupled in the temperature range 5–40 K with 2J = 0.906cm?1, and above 40K it is ferromagnetically coupled with 2J = +7.4cm?1. The effective magnetic moment (μeff) of this complex has been compared with that of a series of other silver(II) complexes available in the literature. Finally, the spectral and magnetic data of this complex have been compared with those of a corresponding isostructural and isomorphous copper(II) complex.
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