Article
Inorganic Chemistry, Vol. 48, No. 23, 2009 11197
account for the appearance of a broad, structureless, red-
shifted fluorescence mechanism when an aromatic iminodia-
cetate electron acceptor, connected to an anthracene fluor-
ophore by covalent methylene spacers, was titratedwith Zn2þ
ions in aqueous solutions. Other types of ratiometric Zn2þ
ion sensors with red-shifted fluorescence emission spectra
associated with a deprotonation mechanism have been
reported using 6,7-dihydroxycoumarin and 1,2-dihydroxy-
anthraquinone as a ligand in 75% methanol-aqueous buffer
solutions8 and an excited state intramolecular transfer
mechanism in the case of 2-(20-benzene-sulfonamidophe-
nyl)benzimidazole ligand in aqueous solutions.9
molecular recognition,17 and sensing.18 We previously stu-
died several TPA derivatives in which interactions between
the arms of the ligand resulted in excitonic interactions.19 We
have recently reported that a derivative of TPA that contains
an 8-hydroxyquinaldine moiety in one arm forms a highly
fluorescent 1:1 complex with Zn2þ in solution.20 Here we
have synthesized other derivatives of TPA and explored the
spectroscopic characteristics of Zn2þ ion complexes with
compound 3.
Tris(2-pyridylmethyl)amine (TPA, 1), which possesses
four nitrogen atoms for the ligation of a wide variety of
metal ions, has been studied extensively.10 Many derivatives
of TPA have also been described, including tris((6-methyl-
2-pyridyl)methyl)amine,11 tris((6-amino-2-pyridyl)methyl)-
amine,12 tris(2,20-bipyridin-6-ylmethyl)amine,13 and tris(2-
quinolylmethyl)amine.14 Studies of TPA-based tripodal com-
plexes have included metalloprotein models,15 catalysis,16
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