TY - JOUR
T1 - A Novel Ferrocenyl Naphthoquinone Fused Crown Ether as a Multisensor for Water Determination in Acetonitrile and Selective Cation Binding
AU - Dagdevren, Metin
AU - Yilmaz, Ismail
AU - Yucel, Baris
AU - Emirik, Mustafa
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/9/24
Y1 - 2015/9/24
N2 - A multisensor which is based on a novel multifunctional triad molecule, ferrocenyl naphthoquinone fused crown ether (Fc-cnq) bearing ferrocene, quinone, and crown ether functional groups together, was synthesized and characterized in this study. Sensing performance of a trace amount of water and the selective cation binding capabilities of this multisensor were carried out by the electrochemical, spectroelectrochemical, and spectrophotometric titration techniques in acetonitrile (CH3CN). It was shown that the potential separation (E(Fc)1/2 - E(2)1/2) between the second reduction of naphthoquinone and the oxidation processes of ferrocene in the triad molecule Fc-cnq was proportional to the amount of water due to the hydrogen-bonding interactions between water and the doubly reduced species (Fc-cnq2-). This property enabled Fc-cnq to detect the trace amount of water in CH3CN. The half-wave potential (E(Fc)1/2) of the ferrocene in Fc-cnq was used as an internal reference potential, and it defined the accuracy of the detection. In addition, by using the UV-vis spectrophotometric titration technique in CH3CN, it was also shown that the Fc-cnq multisensor could bind Ba2+ and Ca2+ cations selectively. We proposed that the intramolecular charge-transfer (CT) transition which occurred between the donor ferrocene and the acceptor naphthoquinone was the principle mechanism for the selective binding property of this multisensor. Quantum chemical calculations were also performed to investigate optical and electronic properties of the Fc-cnq molecule.
AB - A multisensor which is based on a novel multifunctional triad molecule, ferrocenyl naphthoquinone fused crown ether (Fc-cnq) bearing ferrocene, quinone, and crown ether functional groups together, was synthesized and characterized in this study. Sensing performance of a trace amount of water and the selective cation binding capabilities of this multisensor were carried out by the electrochemical, spectroelectrochemical, and spectrophotometric titration techniques in acetonitrile (CH3CN). It was shown that the potential separation (E(Fc)1/2 - E(2)1/2) between the second reduction of naphthoquinone and the oxidation processes of ferrocene in the triad molecule Fc-cnq was proportional to the amount of water due to the hydrogen-bonding interactions between water and the doubly reduced species (Fc-cnq2-). This property enabled Fc-cnq to detect the trace amount of water in CH3CN. The half-wave potential (E(Fc)1/2) of the ferrocene in Fc-cnq was used as an internal reference potential, and it defined the accuracy of the detection. In addition, by using the UV-vis spectrophotometric titration technique in CH3CN, it was also shown that the Fc-cnq multisensor could bind Ba2+ and Ca2+ cations selectively. We proposed that the intramolecular charge-transfer (CT) transition which occurred between the donor ferrocene and the acceptor naphthoquinone was the principle mechanism for the selective binding property of this multisensor. Quantum chemical calculations were also performed to investigate optical and electronic properties of the Fc-cnq molecule.
UR - http://www.scopus.com/inward/record.url?scp=84942315804&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.5b06590
DO - 10.1021/acs.jpcb.5b06590
M3 - Article
C2 - 26352463
AN - SCOPUS:84942315804
SN - 1520-6106
VL - 119
SP - 12464
EP - 12479
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 38
ER -