title: Protonation and coordination properties towards Zn(II), Cd(II) and Hg(II) of a phenanthroline-containing macrocycle with an ethylamino pendant arm.
abstract: Protonation and Zn(II), Cd(II) and Hg(II) coordination with the ligand 5-aminoethyl-2,5,8-triaza-[9]-10,23-phenanthrolinophane (L2), which contains an aminoethyl pendant attached to a phenanthroline-containing macrocycle, have been investigated by means of potentiometric, 1H NMR and spectrofluorimetric titrations in aqueous solutions. The coordination properties of L2 are compared with those of the ligand 2,5,8-triaza-[9]-10,23-phenanthrolinophane (L1). Ligand protonation occurs on the aliphatic amine groups and does not involve directly the heteroaromatic nitrogens. The fluorescence emission properties of L2 are controlled by the protonation state of the benzylic nitrogens: when not protonated, their lone pairs are available for an electron transfer process to the excited phenanthroline, quenching the emission. As a consequence, the ligand is emissive only in the highly charged [H3L2]3+ and [H4L2]4+ species, where the benzylic nitrogens are protonated. Considering metal complexation, both [ML1]2+ and [ML2]2+ complexes (M = Zn(II) and Cd(II)) are not emissive, since the benzylic nitrogens are weakly involved in metal coordination, and, once again, they are available for quenching the fluorescence emission. Protonation of the L2 complexes to give [MHL2]3+ species, instead, leads to a recovery of the fluorescence emission. Complex protonation, in fact, occurs on the ethylamino group and gives a marked change of the coordination sphere of the metals, with a stronger involvement in metal coordination of the benzylic nitrogens; consequently, their lone pairs are not available for the process of emission quenching.
authors.affiliation: Dipartimento di Chimica, Polo Scientifico, Università di Firenze, Via della Lastruccia 3, 50019 Sesto Fiorentino, Firenze, Italy.
authors.forename: Carla
authors.initials: C
authors.lastname: Bazzicalupi
authors.forename: Andrea
authors.initials: A
authors.lastname: Bencini
authors.forename: Emanuela
authors.initials: E
authors.lastname: Berni
authors.forename: Antonio
authors.initials: A
authors.lastname: Bianchi
authors.forename: Lucia
authors.initials: L
authors.lastname: Borsari
authors.forename: Claudia
authors.initials: C
authors.lastname: Giorgi
authors.forename: Barbara
authors.initials: B
authors.lastname: Valtancoli
authors.forename: Carlos
authors.initials: C
authors.lastname: Lodeiro
authors.forename: João Carlos
authors.initials: JC
authors.lastname: Lima
authors.forename: A Jorge
authors.initials: AJ
authors.lastname: Parola
authors.forename: Fernando
authors.initials: F
authors.lastname: Pina
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005021:Ethylamines / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008628:Mercury / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010618:Phenanthrolines / Q000737:chemistry*; D011522:Protons; D015032:Zinc / Q000737:chemistry*
chemical_list: D005021:Ethylamines; D008024:Ligands; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D010618:Phenanthrolines; D011522:Protons; D003300:Copper; D008628:Mercury; D015032:Zinc; C041564:ethylamine