EPR of dynamic Jahn-Teller distortion in CuII doped magnesium Tutton's salt

Rao, P. Sambasiva; Viswanath, Annamraju Kasi; Subramanian, S.

doi:10.1016/0584-8539(92)80248-u

Cited by 38 publications

(25 citation statements)

References 28 publications

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“…The data, listed along with ACDZ, ACDC and Tutton's salts are provided in Table-4. It is interesting to note that the substitution of NH4 + ion by K + ion decreases the δ1,2 values, a trend observed in Tutton's salts [2,51,52]. While ACDC gives a value of 190 cm -1 while PCDC yields only 127 cm -1 .…”

Section: Resultsmentioning

confidence: 82%

Crystal Structure and EPR Studies of Potassium Catena-µ-dichromatodiammine cuprate and Dynamic Behaviour of Cu(II) Doped Potassium Catena-µ-dichlorodiammine-cadmium(II)

Vijayaraj¹,

Jawahar²,

Anantharam³

et al. 2017

Asian J. Chem.

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Octahedral or near octahedral complexes have been subjected to intense investigation, due to their role in understanding the different models of Jahn Teller distortions, viz., dynamic, static and tunneling [1-9]. Most of the copper complexes exhibit tetragonally elongated octahedral geometries, due to J-T vibronic coupling. The compressed geometry observed in a few cases, is in fact, due to the ligand field or steric strain [10]. Intrinsic J-T coupling of Cu 2+ ion completes with the crystal lattice strain effect and results in dynamic J-T property [10-15]. Temperature dependent EPR spectroscopy has been employed to study such dynamic J-T behaviour [16]. Dynamic J-T effect, called as pseudo J-T effect is observed in Cu 2+ ions, present in a site of lower symmetry [17,18]. Such dynamic behaviour is explained using different theoretical models. Complexes, reported to have tetragonally compressed geometry and d z 2 ground state, were found to result from the dynamic equilibrium between the long and intermediate bonds of the tetragonally elongated octahedra with d x 2-y 2 ground state, leading to plasticity [14]. Under the fluxional model [2], the observed stereochemistry at a particular temperature is determined by the relative thermal population of the three available potential energy wells. Each of the well corresponds to an elongated octahedron, misaligned in three mutually perpendicular directions. Hopping

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Section: Resultsmentioning

confidence: 82%

Crystal Structure and EPR Studies of Potassium Catena-µ-dichromatodiammine cuprate and Dynamic Behaviour of Cu(II) Doped Potassium Catena-µ-dichlorodiammine-cadmium(II)

Vijayaraj¹,

Jawahar²,

Anantharam³

et al. 2017

Asian J. Chem.

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“…Among these amphiboles, richterite has a structure where three out of four octahedral sites have axial distortion. Such sites exhibit an ideal geometry for Cu(II) as the Jahn-Teller cation (Rao et al, 1992). This suggests that Cu(II) associated with hectorite can easily be transformed to axial sites of richterite.…”

Section: Spectroscopic Evidence For the Conversion Of Hectoritementioning

confidence: 99%

The transformation of synthetic hectorite in the presence of Cu(II)

Fischer

Weidler

Grobéty

et al. 2009

Clays and clay miner.

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Abstract-The influence of Cu(II) on the hydrothermal and thermal transformations of a synthetic hectorite was investigated by a combined approach using mainly X-ray diffraction, thermal analyses, and electron paramagnetic resonance spectroscopy. The presence of Cu(II) during hydrothermal treatment increased the crystallite size. Copper (II) was both structure-bound and associated with the inner surfaces of the particles. Upon heating, structural destabilization of the hectorite began at~400ºC as indicated by the formation of free radicals. Between 600 and 700ºC, the hectorite converted to enstatite, and in the presence of Cu(II), to enstatite and richterite. The formation of richterite as an additional conversion product is explained by the creation of structural weakness due to structure-bound Cu(II) in F-containing hectorite. Our results suggest that traces of Cu(II), typical of natural environments, may influence the conversion products in high-temperature geochemical systems.

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“…A few salient studies at other EPR centres are summarized below. Cu 2+ : Magnesium Tutton salt -two distinct Cu 2+ ions with dynamic Jahn Teller (JT) distortion at all temperatures; at low temperatures three degenerate vibronic states exist and JT stabilization energy and lattice strain parameters have been determined (60 ). Mn 2+ : (NH 4 )2SbF 5 -There is a doubling of the expected single site; and hfs seen only from basal fluorines; a +20° rotation of the MnF 5 3 " moiety about the crystallographic axis is suggested (61).…”

Section: Centres Produced By Doping In the Solid Statementioning

confidence: 99%

Epr: The Indian Scene

Venkataraman¹

1998

Foundations of Modern EPR

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EPR of dynamic Jahn-Teller distortion in CuII doped magnesium Tutton's salt

Cited by 38 publications

References 28 publications

Crystal Structure and EPR Studies of Potassium Catena-µ-dichromatodiammine cuprate and Dynamic Behaviour of Cu(II) Doped Potassium Catena-µ-dichlorodiammine-cadmium(II)

Crystal Structure and EPR Studies of Potassium Catena-µ-dichromatodiammine cuprate and Dynamic Behaviour of Cu(II) Doped Potassium Catena-µ-dichlorodiammine-cadmium(II)

The transformation of synthetic hectorite in the presence of Cu(II)

Epr: The Indian Scene

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