Temperature dependence of the structure and bonding in deuterated Cu(II) Tutton's salt

Hathaway, B. J.; Hewat, A.W.

doi:10.1016/0022-4596(84)90353-0

Cited by 51 publications

(84 citation statements)

References 12 publications

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“…1). The question has no obvious answer, since more stronger hydrogen bonds between fluorine atoms and water molecules are expected and indeed observed in fluoroberyllates [10], and moreover a weakening of the hydrogen bonds in (ND4)2Cu(SO4)2 • 6D2O results in a switching of the elongation direction from Cu-O(7) to Cu-O(8) bond [1]. We will discuss and answer this question on the basis of our EPR data.…”

Section: Introductionmentioning

confidence: 87%

“…The Tutton salts form an isostuctural series of monoclinic crystals of the general formula M ' 2 M"A 2 • 6H2O, where M' = NH4, K, Rb, Cs, TI; M" = Zn, Cu, Cd, Co, Mn, Ni and A = SO4 , SeO4 , BeF4 , with very close crystal unit cell dimensions within the whole family and α : b : c ratio approximately equal to 3 : 4 : 2, and monoclinic angle β = 1 0 5° [ 1 ] . S i n c e t h e p i o n e e r i n g w o r k o f Bleaney et al [2] there is a constant interest in EPR studies of paramagnetic Cu(II) Tutton salts as well as of diamagnetic salts doped with copper(II) ions.…”

Section: Introductionmentioning

confidence: 99%

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Vibronic Effects in EPR Spectra of (NH₄)₂Cu(BeF₄)₂·6H₂0 Single Crystal

Hoffmann

Gomółka-Marciniak

1993

Acta Phys. Pol. A

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Angular variations of the g-factors and linewidth value were recorded at X-band, at room temperature, and at 77 K. The temperature dependence of the g-factors was measured along the principal g-tensor axes in the temperature range from 4.2 K to 300 K. The rigid lattice g-factors at 4.2 K are: g. = 2.428, gy = 2.138, and gx = 2.058. The gx value very slowly increases linearly on heating, whereas gz and gy nonlinearly tend towards their average value. This is a typical behaviour of Cu(II) EPR in Tutton salt crystals, however the g(T) dependence is much less pronounced in (NH4)2Cu(BeF4)2 •6H20 as compared to the Cu(II) doped salts. The results are described in terms of the two vibronic coupling models of the strong Jahn-Teller effect. It is shown that the models are not adequate to describe the vibronic g-factor behaviour in paramagnetic Cu(II) crystals which is attributed to the cooperative Jahn-Teller effect existing in these crystals.

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Section: Introductionmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Vibronic Effects in EPR Spectra of (NH₄)₂Cu(BeF₄)₂·6H₂0 Single Crystal

Hoffmann

Gomółka-Marciniak

1993

Acta Phys. Pol. A

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“…2). 22 These data show only minor changes on cooling to 156 K, and indicate a Jahn-Teller compressed copper(II) centre. This impression is reinforced by its powder EPR spectrum, which shows a pattern of 60 g-values (g  = 2.20, g || = 2.04).…”

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confidence: 86%

Jahn–Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials

2013

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5This tutorial review discusses the structural and electronic consequences of the Jahn-Teller effect in transition metal complexes, focussing on copper(II) compounds which tend to be the most studied. The nature of a Jahn-Teller distortion in molecular complexes and extended lattices can be manipulated by application of pressure or temperature, by doping a molecule into a host lattice, or simply by molecular design. Many of these results have been achieved using compounds with a trans-[CuX 4 Y 2 ] coordination 10 sphere, which seems to afford copper centres that are particularly sensitive to their environment. JahnTeller distortions lead to some unusual phenomena in molecular magnetism, and are important to the functionality of important classes of conducting and superconducting ceramics.

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“…These were followed by more accurate X-ray diffractometer studies for the copper (Alcock, Duggan, Murray, Tyagi, Hathaway & Hewat, 1984; and nickel (Treushnikov, Kuskov, Soboleva & Belov, 1978;Maslen, Ridout, Watson & Moore, 1988) isomorphs, and by single-crystal neutron diffraction studies at room temperature for the copper (Brown & Chidambaram, 1969; and nickel (Maslen, Ridout, Watson & Moore, 1988) salts. Neutron diffraction determinations were also performed at 4-2 K for the deuterated vanadium (Deeth, Figgis, Forsyth, Kucharski & Reynolds, 1989), hydrogenous manganese (Fender, Figgis, Forsyth, Reynolds & Stevens, 1986), deuterated iron (Figgis, Kucharski, Reynolds & Tasset, 1989), and both hydrogenous and deuterated nickel (Fender, Figgis & Forsyth, 1986a) compounds; a study of the deuterated copper salt by powder neutron diffraction between 5 and 295 K is reported in Hathaway & Hewat (1984).…”

Section: Introductionmentioning

confidence: 99%

“…The present study of the chromium(II) compound has also been carried out in connection with charge density and spin density; we plan to examine spin density later. © 1990 International Union of Crystallography A complication concerning the cation in the CuII salt has been investigated by Alcock et al (1984), Hathaway & Hewat (1984) and Riley, Hitchman & Mohammed (1987). There are unusual Cu--O bondlength changes, and probably an impending phase transition associated with large librational motion of the perdeuteroammonium ions, possibly involving disorder.…”

Section: Introductionmentioning

confidence: 99%