Analytical Sciences

Abstract − Analytical Sciences, 27(5), 511 (2011).

Potential Aluminium(III)- and Gallium(III)-selective Optical Sensors Based on Porphyrazines
Tomasz GOSLINSKI,* Ewa TYKARSKA,* Michal KRYJEWSKI,** Tomasz OSMALEK,** Stanislaw SOBIAK,* Maria GDANIEC,*** Zbigniew DUTKIEWICZ,* and Jadwiga MIELCAREK**
*Department of Chemical Technology of Drugs, Poznan University of Medical Sciences, Grunwaldzka 6, 60-780 Poznan, Poland
**Department of Inorganic and Analytical Chemistry, Poznan University of Medical Sciences, Grunwaldzka 6, 60-780 Poznan, Poland
***Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
Porphyrazines possessing non-coordinating alkyl (propyl) and aralkyl (4-tert-butylphenyl) groups in the periphery were studied as optical sensors for a set of mono-, di- and trivalent cations. Investigated porphyrazines in the UV-Vis monitored titrations revealed significant responses towards aluminium and gallium cations, unlike other metal ions studied. Additionally, porphyrazine possessing 4-tert-butylphenyl peripheral substituents showed sensor property towards ruthenium cation and was chosen for further investigation. The presence of isosbestic points in absorption spectra for its titration with aluminium, gallium and ruthenium cations, accompanied by a linear Benesi–Hildebrand plot, proved complex formation. The continuous variation method was used to determine binding stoichiometry in 1:1 porphyrazine-metal ratio. X-Ray studies and density functional theory calculations were employed to investigate octa(4-tert-butylphenyl)porphyrazine structure. The results helped to explain the observed selectivity towards certain ions. Interaction between ion and porphyrazine meso nitrogen in a Lewis acid–Lewis base manner is proposed.