Analytical Sciences

Abstract − Analytical Sciences, 31(9), 887 (2015).

Influence of Introduced Substituents on the Anion-selectivity of [14]Tetraazaannulene Complexes
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Omiya, Asahi, Osaka 535-8585, Japan
Nickel(II) complexes of [14]tetraazaannulene derivatives incorporating aromatic rings into their azaannulene framework were synthesized, and the anion-selectivity of the [14]tetraazaannulene nickel complexes 14 was evaluated by potentiometric measurements with solvent polymeric membrane electrodes. All of the [14]Tetraazaannulene nickel complexes, except 3, were found to exhibit high selectivity for the I ion over the SCN ion, although considerable interference of the ClO4 ion was observed in all 14 complexes. Concerning the anion-selectivities of 1 and 4, the incorporation of naphthalene rings into the azaannulene framework decreased not only the interference of the ClO4 ion but also the I ion-selectivity over the SCN ion. Comparison studies between the dibenzotetraaza[14]annulene nickel complexes 13 indicated that differences in the attached substituents of the [14]tetraazaannulene nickel complexes greatly influenced the ion-selectivity as ionophores. According to our computational results, the ionophoric properties of [14]tetraazaannulene nickel complexes 14 were influenced by their electrostatic properties rather than their topological properties.