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Abstract
A cyclic, tetra-linked macrocyclic species incorporating four 1,4,8,11-tetraazacyclotetradecane (cyclam) subunits has been synthesized employing Boc amine-group protecting chemistry coupled with high dilution conditions for the cyclization step. A series of 4:1 (metal:ligand (M:L)) complexes with nickel(ii), copper(ii), zinc(ii), and cadmium(ii) has been synthesized. Visible spectophotometric (including spectrophotometric titration), EPR, NMR, and electrochemical studies are reported for individual complexes and are in general accord with similar 4:1 (M:L) coordination behaviour occurring in both the solid state and in solution. The study makes available an example of a new category of large cyclic receptors whose cavity can be tuned electronically through variation of the metal centres incorporated in the cavity walls.
Australian Journal of Chemistry 62(10) 1207–1213 doi:10.1071/CH09312Submitted: 2 June 2009 Accepted: 19 June 2009 Published: 13 October 2009
* Dedicated to the memory of the late Professor A. M. Sargeson FAA, FRS – a great chemist and a true friend for more than 35 years.





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