Zirconium (IV)-3-hydroxy-2-tolyl-4H-chromen-4-one complex-the analytical and DFT studies.

Trace determination of Zr(IV) was carried out by its complexation with a newly synthesized chromone derivative, 3-hydroxy-2-tolyl-4H-chromen-4-one (HToC) for the formation of a 1:4 (M:L) yellow-colored complex from the bicarbonate medium maintained at pH 7.90-8.13. The complex was extractable into the non-aqueous organic solvents showing maximum and stable color intensity in dichloromethane in the wavelength range 414-430 nm. The complex obeyed Beer's law showing linearity of calibration curve in the range 0.0-1.1 µg Zr(IV) ml-1 with an optimum range of determination as 0.44-1.0 ppm Zr(IV) detected from the Ringbom plot. Molar absorptivity, specific absorptivity, and Sandell's sensitivity of thus prepared complex were ascertained, respectively as 4.1971 × 104 l mol-1 cm-1, 0.4601 ml g-1 cm-1, and 0.0022 µg Zr(IV) cm-2 at 420 nm. The linear regression equation being [Formula: see text] (Y = absorbance, X = µg Zr(IV) ml-1) with the correlation coefficient of 0.9977 and detection limit of the procedure as 0.0729 µg ml-1. Theoretical calculations were used to determine and compare structural and bonding properties of the Zr(IV)-HToC complex along with justification of the donor sites provided by ligand for complexation with respect to the metal. The consequences obtained were highly cogent with standard deviation of ± 0.0021 absorbance unit. The procedure was applied to various synthetic (some analogous to cooperate and nickel zirconium) and technical (reverberatory flue dust and water) samples with satisfactory results.