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

Coordination Behaviour of 1-(4,2′:6′,4″-terpyridin-4′-yl)ferrocene and 1-(3,2′:6′,3″-terpyridin-4′-yl)ferrocene: Predictable and Unpredictable Assembly Algorithms*

Y. Maximilian Klein A , Alessandro Prescimone A , Edwin C. Constable A and Catherine E. Housecroft A B
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, University of Basel, Spitalstrasse 51, CH4056 Basel, Switzerland.

B Corresponding author. Email: catherine.housecroft@unibas.ch

Australian Journal of Chemistry 70(5) 468-477 https://doi.org/10.1071/CH16527
Submitted: 22 September 2016  Accepted: 16 October 2016   Published: 4 November 2016

Abstract

The reaction of 1-(4,2′:6′,4″-terpyridin-4′-yl)ferrocene (2) with ZnI2 leads to [{ZnI2(2)}4·1.4MeOH·0.8H2O] which contains a discrete [4+4] metallocycle. Crystal growth experiments demonstrate that reactions of 2 with Zn(OAc)2 or CuCl2 result in the formation of single- or double-stranded 1D polymer chains, respectively, the latter facilitated by the formation of {Cu2Cl4} dinuclear nodes. While both 2 and its isomer 1-(3,2′:6′,3″-terpyridin-4′-yl)ferrocene (3) present V-shaped donor sets, rotation about interannular bonds in 3 generates flexible vectorial properties associated with limiting convergent and divergent orientations of the nitrogen donors. The synthesis and characterisation of 3 are described as are reactions of 3 with ZnCl2 or ZnBr2 which lead, respectively, to a metallosquare in [{ZnCl2(3)}4·3CHCl3·3MeOH] or a helical polymer in [{ZnBr2(3)}·MeOH]n. The tight pitch of the helix in the latter (8.7879(9) Å) is controlled by a combination of the orientations of the N,N″-donor sets in 3, and intra-chain π-stacking interactions involving ferrocenyl and pyridine units.


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