Study On The Recognition Performance Of Ferrocenyl-Based Azines Thioethers And Suophone As Chemosensors Toward Cu²⁺ And Hg²⁺ Ions

In this thesis, we design and synthesized two series of ferrocenyl-based chemosensors, and made detailed study on recognition performance toward metal ions. In the past one, we synthesized seven ferrocenyl-based azines which contained different substituted groups. These chemosensors showed excellent recognition property toward Cu2+ and Hg2+. In addition, we also studied the influence of the substituent groups’electronic and steric effects on the selectivity and sensitivity. In the past two, we synthesized a new type of chemosensors, which were the ferrocenyl-based thioethers. These chemosensors showed excellent recognition property toward Hg2+. Through an oxidation reaction the ferrocenyl-based thioether (containing the -S- unit) turned into ferrocenyl-based sulphone (containing the O=S=O unit). The new chemosensor could recognize Cu2+. The main contents as shown in following:In the past one of the thesis, we synthesized seven ferrocenyl-based sensors containing the -C=N-N=C- as receptor unit by using the simple and efficient method. These chemosensors showed excellent recognition property toward Cu2+ and Hg2+ The Ferrocene-based azines 3f and 5a, which contained the anthryl ring, have shown to be excellent multichannel chemosensors for Hg2+ and Cu2+. The color of the solution containing chemosensor 3f changed from yellow to colorless, upon addition of Hg2+ and Cu2+. Quantification of the absorption titration analysis shows that the detection limit was 6.77 × 10-7 M for 3f-Cu2+,7.19 × 1O-7 M for 3f-Hg2+ and 1.29 × 10-7 M for 5a-Cu2+,2.40 × 10-7 M for 5a-Hg2+, respectively. Compared these datum, we found the 1, 1’-disubstituted ferrocenyl-based azines containing two receptor units (5a) had better recognition property than the 1-substituted ferrocenyl-based azines (3f). In addition, we have found that the electronic and steric effects of the substituted group had obvious influence to the selectivity and sensitivity through the UV-vis titration and the Benesi-Hilderbrand (BH) equation.In the past two of the thesis, we synthesized three ferrocenyl-based chemosensors containing -S- as the receptor unit by using the 2-naphthalenethiol and tosylhydrazone. These new type of chemosensors could recognize Hg2+ through UV-vis and CV, DPV. Quantification of the absorption titration analysis shows that the detection limit was 6.93 × 10-7 M for 4a-Hg2+、4.79 × 10-7 M for 4b-Hg2+ and 9.56× 10-7 M for 4c-Hg2+, respectively. However, when the ferrocenyl-based thioether (containing the -S- unit) was oxidized into ferrocenyl-based sulphone (containing the O=S=O unit), we found that the new chemosensor (5a) could recognize Cu2+ with the color change from colorless to green. The detection limit of 5a could reach 5.22× 10-7 M. In addition, through the test experiments of the recognition property in different pH values, we found chemosensors without nitrogen atom were not easily affected by the acidity and alkalinity.