A rhodamine based chemosensor, 2-(2-(5-bromo-2-hydroxybenzylideneamino)ethyl)-3’,6’-bis(diethylamino)spiro[isoindoline-1,9′-xanthen]-3-one (HL), has been explored for detection of trivalent cations, Al3+, Fe3+ and Cr3+. It has been synthesized by Schiff-base condensation and characterized by standard techniques including X-ray single crystal diffraction analysis. HL is colorless and non-fluorescent. In the presence of trivalent cations, colorless solution of HL turns pink. In UV–vis spectra, gradual addition of the cation produces gradual increment in absorption band at 528nm in HEPES buffer in methanol:water (7:3, v/v) (pH 7.2). No other monovalent and divalent cation except Cu2+ is able to cause color change. HL is almost non-fluorescent in HEPES buffer in methanol:water (7:3, v/v) (pH 7.2) when it is excited at 500nm. Emission intensity increases gradually at 552nm in the presence of increasing concentration of trivalent cations. Intensity increases by 98, 50 and 38 fold in the presence of one equivalent of Al3+, Cr3+ and Fe3+, respectively. No other metal ion can cause an enhancement in emission intensity of HL suggesting selectivity of the probe towards these trivalent cations. Quantum yield of HL complexes with M3+ increases significantly compared to that of free HL. Non-fluorescent HL is a closed ring compound whereas trivalent metal ions induce ring opening of spirolactam ring and complex formation enabling strong fluorescence. Limit of detection (LOD) values of HL have been determined to be 1.18, 1.80 and 4.04nM for Al3+, Cr3+ and Fe3+, respectively, suggesting very high sensitivity towards the cations. Job's plot analysis and mass spectral analysis shows 1:1 complex formation between HL and metal ion. AsO43− ion quenches emission intensity of HL–Al3+ complex as the anion snatches Al3+ from its complex thereby leading to the generation of non-fluorescent spirolactam unit. DFT and TD-DFT studies have been performed to investigate different optimized structures and various spectral transitions. Al3+ complex with HL acts as fluorescent sensor for arsenate ion as the anion snatches Al from Al-HL complex and it returns back to its ring closed spirolactam form. Advanced level molecular logic devices e.g. different 3 and 5 input advanced level logic gates, molecular keypad lock and memory device have been constructed using these properties and interpreted.
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