title: A new pyridine-based 12-membered macrocycle functionalised with different fluorescent subunits; coordination chemistry towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II).
abstract: The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, UK.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Andrea
authors.initials: A
authors.lastname: Bencini
authors.forename: Claudia
authors.initials: C
authors.lastname: Caltagirone
authors.forename: Greta
authors.initials: G
authors.lastname: De Filippo
authors.forename: Luisa Stella
authors.initials: LS
authors.lastname: Dolci
authors.forename: Alessandra
authors.initials: A
authors.lastname: Garau
authors.forename: Francesco
authors.initials: F
authors.lastname: Isaia
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: Palma
authors.initials: P
authors.lastname: Mariani
authors.forename: Luca
authors.initials: L
authors.lastname: Prodi
authors.forename: Marco
authors.initials: M
authors.lastname: Montalti
authors.forename: Nelsi
authors.initials: N
authors.lastname: Zaccheroni
authors.forename: Claire
authors.initials: C
authors.lastname: Wilson