Protonation and coordination properties towards Zn(II), Cd(II) and Hg(II) of a phenanthroline-containing macrocycle with an ethylamino pendant arm

Dalton Transactions : an International Journal of Inorganic Chemistry
Carla BazzicalupiFernando Pina

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...Continue Reading

Citations

Jul 10, 2009·Chemical Society Reviews·Gianluca AccorsiNicola Armaroli
Dec 11, 2007·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·P Muralidhar ReddyVadde Ravinder
Jan 3, 2006·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Mohammad ShakirPoonam Chingsubam
May 19, 2012·International Journal of Molecular Sciences·Puchakayala Muralidhar ReddyVadde Ravinder
Oct 10, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Carla BazzicalupiBarbara Valtancoli
Dec 6, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Carla BazzicalupiBarbara Valtancoli
Jun 10, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Carla BazzicalupiBarbara Valtancoli
Dec 5, 2008·Inorganic Chemistry·Emiliano TamaniniMichael Watkinson

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