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Temperature dependence of the crystal structure and EPR spectrum of bis(1,3,5-trihydroxycyclohexane)copper(II) tosylate. A unified interpretation using a model of dynamic vibronic coupling

Citation

Bebendorf, J and Burgi, HB and Gamp, E and Hitchman, MA and Murphy, A and Reinen, D and Riley, MJ and Stratemeier, H, Temperature dependence of the crystal structure and EPR spectrum of bis(1,3,5-trihydroxycyclohexane)copper(II) tosylate. A unified interpretation using a model of dynamic vibronic coupling, Inorganic Chemistry, 35, (25) pp. 7419-7429. ISSN 0020-1669 (1996) [Refereed Article]

DOI: doi:10.1021/ic960343r

Abstract

The crystal structure of bis(1,3,5-trihydroxycyclohexane)copper(II) tosylate is reported at temperatures of 293, 233,188,163, and 93 K, as are the structures of theZn(II) andNi(II) analogues at room temperature for comparison. The isomorphous compounds are triclinic, space group P1̄, with one formula unit in the unit cell. The unit cell parameters of the Cu compound at 293 K are a = 6.456(5) Å,b = 9.505(3) Å, c = 12.544(3) Å, α = 76.57(2)°, β = 87.48(4)°, γ = 76.65(4)°. The centrosymmetric ZnO6 and NiO6 octahedra are tetragonally compressed with a slight orthorhombic distortion. The Cu2+ polyhedra exhibit similar geometries, but with considerably larger deviations from a regular octahedron. Two of the three independent Cu-O bond lengths and two of the g-values change significantly as a function of temperature. A model of dynamic vibronic coupling is presented which explains both the EPR and structural data. Vibronic wave functions associated with a Jahn-Teller potential energy surface modified by an orthorhombic lattice "strain" are given. The temperature dependence of the structures is calculated from the nuclear parts and that of the g-values from the electronic parts of the wave functions. The temperature dependence of the structures and g-values is also interpreted using a simpler model involving an equilibrium between two forms of the complex which differ solely in their orientation in the crystal lattice, and the results of the two approaches are compared.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Hitchman, MA (Dr Michael Hitchman)
Author:Stratemeier, H (Dr Horst Stratemeier)
ID Code:8615
Year Published:1996
Web of Science® Times Cited:37
Deposited By:Chemistry
Deposited On:1996-08-01
Last Modified:2011-08-19
Downloads:0

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