Basicity and coordination properties of a new phenanthroline-based bis-macrocyclic receptor

Carla Bazzicalupi, Andrea Bencini, Antonio Bianchi, Lucia Borsari, Andrea Danesi, Claudia Giorgi, Carlos Lodeiro, Palma Mariani, Fernando Pina, Samuele Santarelli, Abel Tamayo, Barbara Valtancoli

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


The synthesis and characterisation of the new macrocyclic ligand 6-methyl-2,6,10-triaza-[11]-12,25-phenathrolinophane (L1), which contains a triamine aliphatic chain linking the 2,9 positions of 1,10-phenanthroline and of its derivative L2, composed by two L1 moieties connected by an ethylenic bridge, are reported. Their basicity and coordination properties toward Cu(ii), Zn(ii), Cd(ii), Pb(ii) and Hg(ii) have been studied by means of potentiometric and spectroscopic (UV-Vis, fluorescence emission) measurements in aqueous solutions. L1 forms 1: 1 metal complexes in aqueous solutions, while L2 can give both mono- and dinuclear complexes. In the mononuclear L2 complexes the metal is sandwiched between the two cyclic moieties. The metal complexes with L1 and L2 do not display fluorescence emission, due to the presence of amine groups not involved in metal coordination. These amine groups can quench the excited fluorophore through an electron transfer process. The ability of the Zn(ii) complexes with L1 and L2 to cleave the phosphate ester bond in the presence has been investigated by using bis(p-nitrophenyl)phosphate (BNPP) as substrate. The dinuclear complex with L2 shows a remarkable hydrolytic activity, due to the simultaneous presence within this complex of two metals and two hydrophobic units. In fact, the two Zn(ii) act cooperatively in substrate binding, probably through a bridging interaction of the phosphate ester; the interaction is further reinforced by π-stacking pairing and hydrophobic interactions between the phenanthroline unit(s) and the p-nitrophenyl groups of BNPP.

Original languageEnglish
Pages (from-to)4000-4010
Number of pages11
JournalDalton Transactions
Issue number33
Publication statusPublished - 30 Aug 2006


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