A highly selective chemosensor for cyanide derived from a formyl-functionalized phosphorescent iridium(III) complex

Bejoymohandas, K. S. ; Kumar, Ajay ; Sreenadh, S. ; Varathan, E. ; Varughese, S. ; Subramanian, V. ; Reddy, M. L. P. (2016) A highly selective chemosensor for cyanide derived from a formyl-functionalized phosphorescent iridium(III) complex Inorganic Chemistry, 55 (7). pp. 3448-3461. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem....

Related URL: http://dx.doi.org/10.1021/acs.inorgchem.5b02885

Abstract

A new phosphorescent iridium(III) complex, bis[2′,6′-difluorophenyl-4-formylpyridinato-N,C4′]iridium(III) (picolinate) (IrC), was synthesized, fully characterized by various spectroscopic techniques, and utilized for the detection of CN– on the basis of the widely known hypothesis of the formation of cyanohydrins. The solid-state structure of the developed IrC was authenticated by single-crystal X-ray diffraction. Notably, the iridium(III) complex exhibits intense red phosphorescence in the solid state at 298 K (ΦPL = 0.16) and faint emission in acetonitrile solution (ΦPL = 0.02). The cyanide anion binding properties with IrC in pure and aqueous acetonitrile solutions were systematically investigated using two different channels: i.e., by means of UV–vis absorption and photoluminescence. The addition of 2.0 equiv of cyanide to a solution of the iridium(III) complex in acetonitrile (c = 20 μM) visibly changes the color from orange to yellow. On the other hand, the PL intensity of IrC at 480 nm was dramatically enhanced ∼5.36 × 102-fold within 100 s along with a strong signature of a blue shift of the emission by ∼155 nm with a detection limit of 2.16 × 10-8 M. The cyanohydrin formation mechanism is further supported by results of a 1H NMR titration of IrC with CN-. As an integral part of this work, phosphorescent test strips have been constructed by impregnating Whatman filter paper with IrC for the trace detection of CN- in the contact mode, exhibiting a detection limit at the nanogram level (∼265 ng/mL). Finally, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed to understand the electronic structure and the corresponding transitions involved in the designed phosphorescent iridium(III) complex probe and its cyanide adduct.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:107084
Deposited On:01 Dec 2017 12:36
Last Modified:01 Dec 2017 12:36

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