Synthesis and H+, Cu2+, and Zn2+ coordination behavior of a bis(fluorophoric) bibrachial lariat aza-crown.
The synthesis, protonation behavior, and Cu2+ and Zn2+ coordination chemistry of the novel bibrachial aza lariat ether (naphthalen-1-ylmethyl)[2-(20-[2-[(naphthalen-1-ylmethyl)amino]ethyl]-3,6,9,17,20,23,29,30-octaazatricyclo[23.3.1.1*11,15*]triaconta-1(29),11(30),12,14,25,27-hexaen-6-yl)ethyl]amine (L) are discussed. The macrocycle, which has two aminoethyl naphthyl moieties symmetrically appended to a 2:2 azapyridinophane structure, displays, in the pH range 2-11, six protonation steps that correspond to the protonation of the secondary amino groups. Steady-state fluorescence measurements show emissions due to the monomer and to the excimer formed between the two naphthalene fragments of the macrocycle. The time-resolved fluorescence data, obtained by the time-correlated single photon counting technique, show that a significant percentage of excimer is preformed as ground-state dimers. The ligand L forms with the metal ions Cu2+ and Zn2+ mono- and dinuclear complexes in aqueous solution. The influence of metal coordination in the fluorescence emission of L is analyzed. The acid-base, coordination capabilities, and emissive behavior of L are compared with those presented by its synthetic precursor L1, which has a tripodal tris(2-aminoethyl)amine structure functionalized at one of its terminal amino groups with a naphthyl moiety.
Clares
M Paz
MP
Departament de Química Inorgànica ICMOL, Facultat de Química, Universitat de València, Burjassot, Spain.
Aguilar
Juan
J
Aucejo
Ricardo
R
Lodeiro
Carlos
C
Albelda
M Teresa
MT
Pina
Fernando
F
Lima
J C
JC
Parola
A Jorge
AJ
Pina
João
J
Seixas De Melo
J
J
Soriano
Conxa
C
García-España
Enrique
E
D001372:Aza Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D011522:Protons; D015032:Zinc / Q000737:chemistry*
D001372:Aza Compounds; D011522:Protons; D003300:Copper; D015032:Zinc