Journal
LUMINESCENCE
Volume 37, Issue 8, Pages 1369-1375Publisher
WILEY
DOI: 10.1002/bio.4309
Keywords
electron traps; lanthanide (III) complexes; NBO analysis; quantum chemistry calculations; redox-active ligands; storage materials; thermoluminescence
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Funding
- [FWFN(0205)-2022-0003]
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Thermoluminescent materials and persistent luminescent materials with delayed emission have been widely studied for their potential in optical information storage. In this study, the thermoluminescence mechanism of ternary Ln(NO3)(2)Acac(Phen)(2) complexes (where Ln represents Tb(III), Dy(III), or Eu(III)) was investigated through experimental and theoretical methods. The results showed that the terbium and dysprosium complexes exhibited thermoluminescence properties, while the europium complex did not. The study proposed that the phenanthroline molecules in these complexes act as "chemical" electron traps, allowing for the freezing and storage of the excited state of the complexes. These thermoluminescent materials with "chemical" traps have great potential in optical information storage and anticounterfeiting applications.
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 pi-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.
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