Thermoluminescent Tb(III) and Dy(III) complexes with redox-active ligands: experimental and theoretical study.

Thermoluminescence and persistent luminescent materials with unique delayed emission have attracted much attention and exhibit great promise in optical information storage. In this manuscript, to reveal the thermoluminescence mechanism, a combined experimental and theoretical study of ternary Ln(NO3 )2 Acac(Phen)2 complexes, where Ln is Tb(III), Dy(III), Eu(III), Acac is acetylacetonate anion, and Phen is 1,10-phenanthroline, was carried out. The terbium and dysprosium complexes had thermoluminescence properties, while the europium complex did not. A thermoluminescence mechanism is proposed: the powerful double π-conjugate phenanthroline system appearance upon photoexcitation, the peculiarities of frontier orbitals, the abnormally small highest occupied molecular orbital-lowest unoccupied molecular orbital gap, and the geometrical changes in the terbium and dysprosium complexes led us to suggest that phenanthroline molecules serve as 'chemical' electron traps. Therefore, we succeeded in 'freezing' and storing the excited state of complexes I and II indefinitely. The obtained thermoluminescent materials with 'chemical' traps of electrons are capable of storing the energy from incident photons and exhibit a great opportunity in optical information storage and anticounterfeiting applications.

Luminescent amine sensor based on europium(III) chelate.

The effect of methylamine vapor on luminescence of Eu(III) tris-benzoylacetonate (I) immobilized in thin-layer chromatography plates has been investigated. It has been revealed that interaction of I with analyte vapor results in increase of the intensity of Eu(III) luminescence. The mechanism of the effect of methylamine vapors on intensification of the Eu(III) luminescence has been suggested using the data of IR spectroscopy and quantum chemistry calculations. The mechanism of luminescence sensitization consists in bonding of an analyte molecule with a water molecule into the coordination sphere of Eu(III). As a result, the bond of a water molecule with the luminescence centre weakens, rigid structural fragment including europium ion, water and methylamine molecules forms. The presence of such fragment must naturally promote decrease of influence of OH-vibrations on luminescence of the complex I.

Europium(III) tris-dibenzoylmethanate as an efficient chemosensor for detection of ammonia.

The effect of ammonia vapor on luminescence of Eu(III) tris-dibenzoylmethanate immobilized in various matrices has been investigated. It has been revealed that interaction of Eu(III) tris-dibenzoylmethanate with analyte vapor results in increase of the intensity of Eu(III) luminescence. The mechanism of the effect of ammonia vapors on intensification of the Eu(III) luminescence has been suggested using the data of IR spectroscopy, X-ray diffraction analysis and quantum chemistry calculations. The mechanism of luminescence sensitization consists in bonding of an analyte molecule with a water molecule into the coordination sphere of Eu(III). As a result, the bond of a water molecule with the luminescence centre weakens and the blockage of the quenching of luminescence on OH-vibrations takes place.