Issue 2, 2006
From the journal:

Dalton Transactions

Structural systematics of the [Cu(chelate)3][Y]2 series. An interesting crystallographic structural insight involving vibronic coupling and the Jahn–Teller effect (JTE). The syntheses and low temperature crystal structures of tris(2,2′bipyridyl)copper(ii) tetraphenylborate and tris(2,2′bipyridyl)zinc(ii) tetraphenylborate†‡

Brian Murphy,*a   Moza Aljabri,a   Aaleya Mohamed Ahmed,a   Gillian Murphy,b   Brian J. Hathaway,§b   Mark E. Light,c   Thomas Geilbrichc  and  Michael B. Hursthousec  

* Corresponding authors

a Department of Chemistry, College of Science, United Arab Emirates University, PO Box 17551, Al Ain, United Arab Emirates
E-mail: Murphy.Brian@uaeu.ac.ae
Fax: +971-3-7671291
Tel: +971-3-7134062

b Department of Chemistry, University College Cork, Republic of Ireland

c EPSRC National X-Ray Crystallography Service, Department of Chemistry, University of Southampton, Highfield, Southampton, UK

Abstract

The crystal structures of [Cu(bipy)3][BPh4]2, 1, and [Zn(bipy)3][BPh4]2, 2 have been determined at low temperature. 1 and 2 are closely related, but are not isostructural. Both contain a two-dimensional supramolecular construct (SC) involving a sandwich structure. 1 has a six-coordinate CuN6 chromophore with a regular elongated octahedral stereochemistry and rhombic in-plane bond lengths. The associated tetragonality value, T, of 1 is 0.8868. 2 involves a six-coordinate octahedral chromophore. Differences between 1 and 2 relate to the tendency of copper(II) complexes to undergo a Jahn–Teller (JT) distortion. The zinc(II) cation feels solely the host site strain, whereas the copper(II) cation also involves vibronic JT type coupling. The copper polyhedron geometry is characterized by both phenomena, with the vibronic interaction dominating. Scatter plot analysis involving the tris-chelate copper(II) series suggests that neither pure Qθ or Qε components or the a2u mode operate in isolation over the entire series. All three operate in combination with varying quantifiable contributions, leading to distortion from the regular tetragonal octahedral stereochemistry.

Graphical abstract: Structural systematics of the [Cu(chelate)3][Y]2 series. An interesting crystallographic structural insight involving vibronic coupling and the Jahn–Teller effect (JTE). The syntheses and low temperature crystal structures of tris(2,2′bipyridyl)copper(ii) tetraphenylborate and tris(2,2′bipyridyl)zinc(ii) tetraphenylborate

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Article information

DOI
https://doi.org/10.1039/B509070A
Article type
Paper
Submitted
27 Jun 2005
Accepted
07 Sep 2005
First published
29 Sep 2005

Dalton Trans., 2006, 357-367

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Structural systematics of the [Cu(chelate)3][Y]2 series. An interesting crystallographic structural insight involving vibronic coupling and the Jahn–Teller effect (JTE). The syntheses and low temperature crystal structures of tris(2,2′bipyridyl)copper(II) tetraphenylborate and tris(2,2′bipyridyl)zinc(II) tetraphenylborate

B. Murphy, M. Aljabri, A. M. Ahmed, G. Murphy, B. J. Hathaway, M. E. Light, T. Geilbrich and M. B. Hursthouse, Dalton Trans., 2006, 357 DOI: 10.1039/B509070A

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