Selectivity for La3+ ion by synthesized 4-((5-methylfuran-2-yl)methylene)hydrazono)methyl)phenol receptor and its spectral analysis

Abstract

The functionalized molecules with specific molecular sites appear to be a promising approach for detection of cation in UV-visible and fluorescence spectroscopy. The synthesized receptor 4-((5-methylfuran-2-yl)methylene)hydrazono)methyl)phenol MFMHMP was found selective for La³⁺ among Ag⁺, K⁺, Na⁺, Be²⁺, Mg²⁺, Ca²⁺, Eu³⁺, Al³⁺, La³⁺, Zr⁴⁺, Th⁴⁺, UO₂²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Hg²⁺ metal ions used as their nitrates by UV-visible spectroscopy and fluorescence spectroscopy. The binding nature of MFMHMP with La³⁺ ion was analyzed by UV-visible, fluorescence, IR, mass spectroscopy and cyclic voltammetric studies. The stoichiometry was established to be 1:1 by Benesi-Hildebrand, mole-ratio method and method of continuous variation (Job's method) with good association affinity K = 6.245 × 10⁴ M^-1. Computational studies and Density functional theory (DFT) calculation gives the proof of electron transfer during excitation and emission. Binding energy of complex through Density Function Theory -62.387 kcal/mol has also indication of strong binding. The electron transfer energy of Higher occupied molecular orbital (HOMO) to Lower unoccupied molecular orbital (LUMO) is about 4.662 eV for MFMHMP+La³⁺ Complex. Among that all transitions HOMO → LUMO + 8 and HOMO → LUMO + 9 play a key role for the blue shift transition during complexation.

Keywords: DFT; IR; La(3+); Mass spectroscopy; Sensor; UV–visible.