title: Potential aluminium(III)- and gallium(III)-selective optical sensors based on porphyrazines.
abstract: 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.
authors.affiliation: Department of Chemical Technology of Drugs, Poznan University of Medical Sciences, Poland. tomasz.goslinski@ump.edu.pl
authors.forename: Tomasz
authors.initials: T
authors.lastname: Goslinski
authors.forename: Ewa
authors.initials: E
authors.lastname: Tykarska
authors.forename: Michal
authors.initials: M
authors.lastname: Kryjewski
authors.forename: Tomasz
authors.initials: T
authors.lastname: Osmalek
authors.forename: Stanislaw
authors.initials: S
authors.lastname: Sobiak
authors.forename: Maria
authors.initials: M
authors.lastname: Gdaniec
authors.forename: Zbigniew
authors.initials: Z
authors.lastname: Dutkiewicz
authors.forename: Jadwiga
authors.initials: J
authors.lastname: Mielcarek
mesh_terms: D000535:Aluminum / Q000032:analysis*; D005708:Gallium / Q000032:analysis*; D055096:Optical Devices; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet / Q000295:instrumentation
chemical_list: D011166:Porphyrins; D005708:Gallium; D000535:Aluminum