New ferrocenyl naphthoquinone fused crown ether chemosensors: Highly selective, kinetically and regio controlled colorimetric, beryllium ion recognition

Yusuf Alcay, Ozgur Yavuz, Ali Gelir, Secil Kirlangıc Atasen, Kaan Karaoglu, Baris Yucel, Nurcan Şenyurt Tuzun, Ismail Yilmaz*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)

Abstract

New organometallic chemosensors which are based on triad molecules, ferrocenyl naphthoquinone linearly/angularly fused crown ethers (Fc–cnq–1a and Fc–cnq–1b) bearing ferrocene, quinone, and crown ether functional groups together, were synthesized and utilized for selective sensing trace amount of Be2+ ion (5.41 μM) among other metal cations. The UV–vis spectrophotometric titration experiments at controlled temperatures (25–60 °C) resulted in characteristic spectral changes in the intramolecular charge-transfer (CT) transitions upon addition of Be2+ ion into the solution of sensors Fc–cnq–1a and Fc–cnq–1b. However, no spectral changes were observed for the other metal cations used for testing at the same conditions, indicating that the sensors can selectively detect Be2+ among the studied metal ions even at higher temperatures. The spectral change in the absorption spectra of the sensors upon addition of Be2+ ion corresponds to the visible region of the spectrum, from deep green to yellow color, and this leads to observe the effect of the Be2+ ion with naked eye. The sensors used for the signaling of Be2+ ion displayed a significant shortening in response time depending on increasing temperature without any degradation of the sensors. Fc–cnq–1a displayed faster response time than Fc–cnq–1b in the temperature range of 35–60 °C. The activation energies for the pseudo-first order complexation reactions were calculated as 124.2±13.0 kJ mol−1 and 151.9±18.0 kJ mol−1 for Fc–cnq–1a and Fc–cnq–1b, respectively, which explains faster response time of Fc–cnq–1a for recognizing Be2+ ion. Density Functional Theory calculations (TD-B97D/TZVP//mPWPW91/6-31 + G(2d,2p) level) were performed on Fc–cnq–1a, Fc–cnq–1b and their Be+2 complexes in order to elucidate their geometries and the molecular orbitals. Calculations have shown comparable results with those obtained from the experimental data.

Original languageEnglish
Pages (from-to)131-143
Number of pages13
JournalJournal of Organometallic Chemistry
Volume868
DOIs
Publication statusPublished - 1 Aug 2018

Bibliographical note

Publisher Copyright:
© 2018 Elsevier B.V.

Funding

This work was supported by The Scientific and Technical Research Council of Turkey (TUBİTAK, Project no: 113Z309 ).

FundersFunder number
TUBİTAK
Türkiye Bilimsel ve Teknolojik Araştirma Kurumu113Z309

    Keywords

    • Beryllium
    • Colorimetry
    • Ferrocene
    • Naphthoquinone
    • Sensor

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