Synthesis, Coordination Properties, and Analytical Applications of Mixed Donor Macrocycles Containing the 1,10-Phenanthroline Sub-unit

 V. Lippolis^a,* and M. Shamsipur^b

^aDipartimento di Chimica Inorganica ed Analitica, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato (CA), Italy

^bDepartment of Chemistry, Razi University, Kermanshah, Iran

(Received 22 February 2006, Accepted 12 March 2006)

  The coordination properties towards different metal ions of a new class of mixed N/S-, and N/S/O-donor macrocycles containing the 1,10-phenanthroline sub-unit in the cyclic framework are reviewed. The conformational constraints imposed by the heteroaromatic fragment onto the aliphatic portion of the ring determine the coordination mode of these ligands which can stabilise low-valent Ni⁺, Pd⁺, Pt⁺, and Rh⁺ metal complexes. Structural and thermodynamic aspects of the coordination chemistry of these ligands are considered together with possible applications as building blocks in the synthesis of multi-centred systems, and as template in the construction of extended polyiodide networks. However, solution studies demonstrate the inability of these ligands to work as selective and specific fluorescent chemosensors for heavy transition and post-transition metal ions and the formation constants evaluated for the formation of 1:1 complexes with Pb²⁺, Cd²⁺, Hg²⁺, Cu²⁺, and Ag⁺ in acetonitrile are of the same order of magnitude. Nevertheless, some of these macrocyles are extremely effective to recognise Cu²⁺ or Ag⁺ over the other metal ions in transport processes, and have been successfully used as neutral ionophore in the construction of PVC-based ion-selective electrodes and supported liquid membranes for analytical detection and separation, respectively, of these metal ions.

 Keywords: Macrocyclic ligands, 1,10-Phenanthroline, Coordination properties, Ion-selective electrodes, Supported liquid membranes, Copper(II) and Silver(I)