Synthesis of calix[4]arene derivatives with fluorescent subunits and study of their complexation with alkali-metal cation

Tranfić Bakić, Marina (2015) Synthesis of calix[4]arene derivatives with fluorescent subunits and study of their complexation with alkali-metal cation. Doctoral thesis, Faculty of Science > Department of Chemistry.

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Abstract

In the framework of this work seven fluorescent calix[4]arene derivatives with phenanthridine (1–3) and diphenylanthracene (4–7) substituents at the lower calixarene rim were synthesized. Compounds were prepared by “conventional” organic synthesis as well as by microwave-assisted synthesis, and the reaction times and yields were compared. The compounds were characterized by means of FTIR, 1H and 13C NMR spectroscopies, elemental analysis as well as by mass spectrometry. The complexation of these ligands with alkali-metal cations was studied by spectrophotometric, fluorimetric, potentiometric, and NMR titrations in acetonitrile/dichloromethane and methanol/dichloromethane solvent mixtures (φ = 0.5). The stability constants of the corresponding 1:1 (cation:ligand) complexes were determined. Ion association in these solvent mixtures was also investigated because this phenomenon can considerably affect the complexation process. The ligands were proven to bind the alkali-metal cations rather strongly with lowering of their binding abilities with the increase of the cation radius. It was found that solvent considerably affected the stability of the complexes, whereby the ligands showed significantly higher affinities for cations in acetonitrile than in methanol/dichloromethane mixture. It could be concluded that the prepared calixarene ligands could serve as sensitive fluorimetric sensors for alkali-metal cations.

Item Type: Thesis (Doctoral thesis)
Keywords: alkali metal cations, calixarenes, complexation, fluorescence, fluorimetric titration, NMR, potentiometric titration, solvation, spectrophotometric titration, stability constant
Supervisor: Tomišić, Vladislav and Frkanec, Leo
Date: 2015
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Faculty of Science > Department of Chemistry
Depositing User: Branka Maravic
Date Deposited: 24 Apr 2015 11:39
Last Modified: 24 Apr 2015 11:39
URI: http://digre.pmf.unizg.hr/id/eprint/3887

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