Synthesis of new compartmental amino-phenolic ligands. Basicity, coordination properties towards Cu(II) and Zn(II) ions. A fluorescent chemosensor for H+ and Zn(II)

The syntheses of three new compartmental ligands are reported. Each ligand shows two 1,4,7-triazaheptane (dien) moieties separated by different rigid aromatic groups. The dien unit is linked to the spacer through its central N-atom, while each aromatic moiety contains two hydroxyl-phenolic functions. The synthetic aspects involved in attaching two dien subunits to an aromatic group containing two hydroxyl functions were explored. Each ligand synthesized can coordinate two metal ions positioned far from each other; the single dinuclear units will be useful as building blocks in new supramolecular aggregates. The basicity and binding properties of one of the synthesized ligands (3,3'-bis[N,N-bis(2-aminoethyl)amino-methyl]4,4'-dihydroxybiphenyl (L2)) were potentiometrically studied in aqueous solution. L2 was found to behave as a diprotic acid and as a pentaprotic base under the experimental conditions used. L2 forms stable mononuclear and dinuclear complexes with Cu(II) and Zn(II) ions; the mononuclear species show a tendency to dimerize, while the dinuclear ones are predominant in the presence of two equivalents of M(II) ions in solution. Both protonation and the presence of Zn(II) strongly affect the fluorescence emission properties of L2, which can be used as a new chemosensor for H+ and Zn(II) ions. L2 exhibits pH-dependent fluorescence and the emission due to the different protonation of L2 and can be ascribed, above all, to the degree of protonation of the 4,4'-biphenol unit; thus, L2 is more emitting at acidic pH values where the aromatic unit is fully protonated. On the contrary, the Zn-dinuclear species are more emitting from neutral to alkaline pH values exhibiting a CHEF effect which reaches its maximum values (seven times those of the free ligand) at pH 9 with the [Zn2H L-2(2)](2+) species, thus highlighting the sensing properties of this new chemosensor towards Zn(II). (C) 2008 Elsevier B.V. All rights reserved.