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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Solvent-Induced Structural Changes in Complexes of 1,2-Bis(3-(3-pyridyl)pyrazolyl)ethane

Yuniar P. Prananto A , David R. Turner A , Jinzhen Lu A and Stuart R. Batten A B
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A School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.

B Corresponding author. Email: stuart.batten@sci.monash.edu.au

Australian Journal of Chemistry 62(2) 108-114 https://doi.org/10.1071/CH08483
Submitted: 5 November 2008  Accepted: 7 December 2008   Published: 19 February 2009

Abstract

A series of complexes have been obtained using the flexible ditopic ligand 1,2-bis(3-(3-pyridyl)pyrazolyl)ethane (LEt) with M(SCN)2 (M = Co, Fe) and ZnCl2. The ligand is observed to exist in a variety of conformations with rotations around the ethane spacer and around the pyridyl/pyrazole bond. The bridging length of the ligand (i.e., distance between pyridyl nitrogen atoms) varies by 3.5 Å depending on its geometry. Three different cobalt(ii) complexes of the general form [Co(LEt)2(SCN)2]·Solv (where Solv is a variable number/type of non-coordinated solvent) have been structurally characterized and form a series of solvent dependant supramolecular isomers. When Solv = 2MeCN a (4,4)-sheet is formed (1), however, when Solv = H2O an alternate ‘collapsed’ (4,4)-sheet is observed (2). Changing the solvent to two molecules of N,N-dimethylformamide (DMF) leads to a radical change in structure with a one-dimensional (1D) polymer formed (3) that contains two bridging ligands between adjacent metal atoms (i.e., maintaining the same metal/ligand ratio as in the (4,4)-sheet structures). A monomeric thiocyanate complex [Fe(LEt)2(SCN)2(H2O)2] (4) is reported in which the bispyridyl ligands are terminal and partake in an extended hydrogen-bonded network. A 1D polymer [Zn(LEt)Cl2] (5) is also presented. The structures of the metal complexes are contrasted with that of the free ligand.


Acknowledgements

The authors thank the Australian Research Council for funding and for a post-doctoral fellowship (D.R.T.). Y.P.P. acknowledges an ADS scholarship.


References


[1]   Steed J. W., Turner D. R., Wallace K. J., Core Concepts in Supramolecular Chemistry and Nanochemistry 2007 (John Wiley and Sons: Chichester).

[2]   Batten S. R., Neville S. M., Turner D. R., Coordination Polymers: Design, Analysis and Application 2008 (Royal Society of Chemistry: Cambridge).

[3]   S. R. Batten, J. Solid State Chem. 2005, 178,  2475.
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