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Fluorene Based Ferric Complex as Colorimetric and Fluorometric Probe for Highly Selective Detection of CN− and S2− Anions

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Abstract

A series of new chemosensor molecules bearing benzothiazole-, quinoline- and phthalazine-functionalized fluorene derivatives were synthesized and their complexation behaviors with Fe3+ and Sn2+ ions were investigated. The sensing abilities of their complexes towards both cyanide and sulfide anions were investigated by colorimetric and fluorometric techniques in detail. The sensing mechanism was investigated by Job’s and Scatchard plots evaluations, and also absorption/fluorescence titration experiments. Among the studied dye/metal binary systems, F-BT sensor to Fe3+ giving the detection limits of 3.1 µg has also displayed high selectivity and sensitivity towards CN− and S2− anions, lead to a significant color change of the solution observable by the naked eye.

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Acknowledgements

This work was supported by the Research Council of Manisa Celal Bayar University with the project number of 2018 − 126.

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The funder has been acknowledged in the acknowledgement section.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Arts and Science, Manisa Celal Bayar University, Yunus Emre, 45140, Manisa, Turkey

    Gözde Murat Saltan & Haluk Dinçalp

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  1. Gözde Murat Saltan
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Gözde Murat Saltan and Haluk Dinçalp made substantial contribution while preparing the manuscript.

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Correspondence to Haluk Dinçalp.

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Supplementary Information

ESM 1

Illustration of CT possibilities of F-PHT, F-BT, and F-QU dyes on their first HOMO and LUMO energy orbitals calculated by using density functional theory (DFT) [44] at the B3LYP/6-31G(d) [45] basis with the Gaussian 09 package (JPG 45 kb)

ESM 2

Cyclic voltammograms of F-PHT, F-BT, and F-QU dyes on glassy carbon working electrode in 0.1 M [TBA][PF6]/MeCN (Scan rate: 100 mV s─1) (JPG 523 kb)

ESM 3

Optical absorption changes of (a) F-PHT (2 × 10−5 M) and (b) F-QU (2 × 10−5 M in MeCN solution in the presence of different metal ions at saturated concentrations (JPG 717 kb)

ESM 4

(JPG 742 kb)

ESM 5

Changes in UV–vis absorption and fluorescence emission spectra (inset) of F-PHT at the initial concentrations of 2 × 10−5 M in MeCN solution by the titration upon addition of (a) Sn2+ (0 to 26.0 × 10−5 M), and (b) Fe3+ ions (0 to 42.0 × 10−6 M) indicated by arrow (λexc = 375 nm) (JPG 682 kb)

ESM 6

(JPG 738 kb)

ESM 7

Changes in UV–vis absorption and fluorescence emission spectra (inset) of F-QU at the initial concentrations of 2 × 10−5 M in MeCN solution by the titration upon addition of (a) Sn2+ (0 to 26.0 × 10−5 M), and (b) Fe3+ ions (0 to 42.0 × 10−6 M) indicated by arrow (λexc = 375 nm) (JPG 698 kb)

ESM 8

(JPG 682 kb)

ESM 9

Job’s plots for (a) F-PHT/Sn2+, (b) F-PHT/Fe3+, (c) F-QU/Sn2+, (d) F-BT/Sn2+, (e) F-BT/Fe3+ complex in MeCN solution (The total concentration of each was 2 × 10−5 M) (JPG 450 kb)

ESM 10

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ESM 11

(JPG 446 kb)

ESM 12

(JPG 471 kb)

ESM 13

(JPG 422 kb)

ESM 14

Scatchard plot for (a) F-PHT/Sn2+ (F−F0/[Sn2+] = −7.33 × 103(F − F0) + 6.5 × 107; R2: 0.89), and (b) F-BT/Sn2+ (F−F0/[Sn2+] = −2.11 × 103(F − F0) + 2.4 × 107; R2: 0.94) complex in MeCN solution (JPG 426 kb)

ESM 15

(JPG 406 kb)

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Murat Saltan, G., Dinçalp, H. Fluorene Based Ferric Complex as Colorimetric and Fluorometric Probe for Highly Selective Detection of CN− and S2− Anions. J Fluoresc 31, 1311–1321 (2021). https://doi.org/10.1007/s10895-021-02737-w

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