Highly luminescent Tb(III) macrocyclic complex based on a DO3A hosting unit and an appended carboxylated N,C-pyrazolylpyridine antenna

Nasso, Isabelle; Geum, Neri; Bechara, Ghassan; Mestre-Voegtle, Béatrice; Galaup, Chantal; Picard, Claude

doi:10.1016/j.jphotochem.2013.10.005

Cited by 11 publications

(4 citation statements)

References 51 publications

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“…Experimental studies have revealed that the energy gap between the emitting level of Tb(III) ion ( 5 D 4 state) and T 1 state of less than 1850 cm −1 promotes fast BET and low luminescence efficiency343738. Consequently, Tb(III) complexes with high luminescence efficiency use organic ligands with high T 1 state energy and therefore even higher singlet excited (S 1 ) state energy, leading to absorption range shorter than 350 nm343940. Expanding this range to a longer wavelength while maintaining high luminescence efficiency leads to a larger degree of freedom in molecular design, allowing incorporation of functionality, such as sensing, chirality, and self-assembly.…”

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confidence: 99%

Critical Role of Energy Transfer Between Terbium Ions for Suppression of Back Energy Transfer in Nonanuclear Terbium Clusters

Omagari

Nakanishi

Kitagawa

et al. 2016

Sci Rep

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Lanthanide (Ln(III)) complexes form an important class of highly efficient luminescent materials showing characteristic line emission after efficient light absorption by the surrounding ligands. The efficiency is however lowered by back energy transfer from Ln(III) ion to the ligands, especially at higher temperatures. Here we report a new strategy to reduce back energy transfer losses. Nonanuclear lanthanide clusters containing terbium and gadolinium ions, TbnGd9−n clusters ([TbnGd9−n(μ-OH)10(butylsalicylate)16]+NO3−, n = 0, 1, 2, 5, 8, 9), were synthesized to investigate the effect of energy transfer between Tb(III) ions on back energy transfer. The photophysical properties of TbnGd9−n clusters were studied by steady-state and time-resolved spectroscopic techniques and revealed a longer emission lifetime with increasing number of Tb(III) ions in TbnGd9−n clusters. A kinetic analysis of temperature dependence of the emission lifetime show that the energy transfer between Tb(III) ions competes with back energy transfer. The experimental results are in agreement with a theoretical rate equation model that confirms the role of energy transfer between Tb(III) ions in reducing back energy transfer losses. The results provide a new strategy in molecular design for improving the luminescence efficiency in lanthanide complexes which is important for potential applications as luminescent materials.

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confidence: 99%

Critical Role of Energy Transfer Between Terbium Ions for Suppression of Back Energy Transfer in Nonanuclear Terbium Clusters

Omagari

Nakanishi

Kitagawa

et al. 2016

Sci Rep

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“…The radiative rate constant k r was estimated from the emission lifetime at 100 K under the assumption that the lifetime at low temperature is purely radiative (i.e., the nonradiative rate constant k nr is negligible). While this simplification is not accurate, it allows a direct comparison of the rate constants of the clusters if the difference in the values is large enough. , The results are summarized in Table . The k r values for Tb-L1, Tb-L2, and Tb-L3 were calculated to be 696, 823, and 654 s –1 , respectively.…”

Section: Results and Discussionmentioning

confidence: 99%

Effective Photosensitized Energy Transfer of Nonanuclear Terbium Clusters Using Methyl Salicylate Derivatives

et al. 2015

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The photophysical properties of the novel nonanuclear Tb(III) clusters Tb-L1 and Tb-L2 involving the ligands methyl 4-methylsalicylate (L1) and methyl 5-methylsalicylate (L2) are reported. The position of the methyl group has an effect on their photophysical properties. The prepared nonanuclear Tb(III) clusters were identified by fast atom bombardment mass spectrometry and powder X-ray diffraction. Characteristic photophysical properties, including photoluminescence spectra, emission lifetimes, and emission quantum yields, were determined. The emission quantum yield of Tb-L1 (Φ(ππ*) = 31%) was found to be 13 times larger than that of Tb-L2 (Φ(ππ*) = 2.4%). The photophysical characterization and DFT calculations reveal the effect of the methyl group on the electronic structure of methylsalicylate ligand. In this study, the photophysical properties of the nonanuclear Tb(III) clusters are discussed in relation to the methyl group on the aromatic ring of the methylsalicylate ligand.

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“…17 However, the majority of terbium complexes with aromatic carboxylic acid has difficulty in matching 365 nm UV chip. 19 Guo and coworkers prepared terbium complex containing benzoic acid with excitation band between 250~360 nm. 18 Wu et al reported terbium complex of 6-methyl-2-(3-ethoxycarbonylpyrazol-1-yl)pyridine with the optimal excitation wavelength at 301 nm.…”

Section: Introductionmentioning

confidence: 99%

“…18 Nasso et al reported a terbium complex of 6-methyl-2-(3-ethoxycarbonylpyrazol-1-yl)pyridine with the an optimal excitation wavelength at 301 nm. 19 Guo and co-workers prepared a terbium complex containing benzoic acid with an excitation band between 250-360 nm. 20 These terbium complexes demand further improvement to meet excitation by a 365 nm UV chip.…”

Section: Introductionmentioning

confidence: 99%

Tunable white light emission of Eu,Tb,Zn-containing copolymers by RAFT polymerization

Zhang

Sun

et al. 2015

J. Mater. Chem. C

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In this work, a novel copolymer PS-Eu-Tb-Zn, which can match 365 nm UV chip, was synthesized by RAFT polymerization of Tb(p-BBA) 3 UA, Eu(TTA) 2 (Phen)MAA, Zn(BTZ)UA and styrene. TG-DTG and PL analyses indicate that copolymer PS-Eu-Tb-Zn displays favorable thermal stability and luminescent properties. Excited at 365 nm, the copolymer exhibits emission peaks at 421 nm (blue emission), 488, 543 nm (green emission), 589 and 615 nm (red emission). The white light of the copolymer can be obtained by tuning the ratios of three complexes and excitation wavelengths. The CIE coordinates (0.352, 0.330) of the copolymer is optimal upon excitation at 365 nm. For the fabricated white LED using 365 nm UV chip with the copolymer, the CCT is 5684 K, and the CRI is 83.1. All the results indicate that the copolymer can be applied as a phosphor for fabrication of NUV-based white LED.performance. Moreover, the optical properties of the fabricated WLED also show that the CCT is 5684 K, the CRI (R a ) is 83.1. In comparison with the WLED based on blue InGaN chip and YAG:Ce 3+ phosphor (R a =75, CCT=7756 K), 62,63 the WLED in this study shows higher R a value and lower CCT value, indicating copolymer 5 can be a promising candidate for application in NUV-based white LED.

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Highly luminescent Tb(III) macrocyclic complex based on a DO3A hosting unit and an appended carboxylated N,C-pyrazolylpyridine antenna

Cited by 11 publications

References 51 publications

Critical Role of Energy Transfer Between Terbium Ions for Suppression of Back Energy Transfer in Nonanuclear Terbium Clusters

Critical Role of Energy Transfer Between Terbium Ions for Suppression of Back Energy Transfer in Nonanuclear Terbium Clusters

Effective Photosensitized Energy Transfer of Nonanuclear Terbium Clusters Using Methyl Salicylate Derivatives

Tunable white light emission of Eu,Tb,Zn-containing copolymers by RAFT polymerization

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