Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield

Latva, Martti; Takalo, Harri; Mukkala, Veli-Matti; Mãtãchescu, Cristina; Rodríguez‐Ubis, Juan Carlos; Kankare, Jouko

doi:10.1016/s0022-2313(97)00113-0

Cited by 1,599 publications

(1,236 citation statements)

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“…31,43 For the Tb-5LI-IAM-X complexes,  values decrease gradually as the T 0-0 -5 D 4 energy gap is lowered from ~ 3,500 cm -1 (Tb-Amide) to ~ 1,600 cm -1 (Tb-CH 3 ), and then plummet when the energy gap shrinks to ~ 600 cm -1 (Tb-F). Latva and coworkers observed a similarly sharp drop-off in quantum yield values as the antenna triplet energies went below ~22000 cm -1 .…”

Section: Resultsmentioning

confidence: 99%

“…The 5LI-IAM-OCH 3 triplet state is more than 500 cm -1 below the 5 D 4 emitting state and is therefore not expected to sensitize Tb(III) emission at room temperature. 31 The Hammett substitutent parameters, 39  p , and the inductive/field (F) and resonance (R) component parameters were examined to see if they correlated with the absorption and emission energies of the IAM chromophores. Such a correlation would provide a preliminary strategy for IAM-ligand design.…”

Section: Resultsmentioning

confidence: 99%

“…Latva and coworkers observed a similarly sharp drop-off in quantum yield values as the antenna triplet energies went below ~22000 cm -1 . 31 Although looking at energy transfer efficiency only in terms of the antenna triplet levels is an oversimplification of the energy transfer process, the T 0-0 -5 D 4 relationship is nonetheless a useful trend to guide ligand design, especially when looking at a single class of antenna ligands.…”

Section: Resultsmentioning

confidence: 99%

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Predicting Efficient Antenna Ligands for Tb(III) Emission

Samuel

Raymond

2008

Inorg. Chem.

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ABSTRACT:A series of highly luminescent Tb(III) complexes of para-substituted 2-hydroxyisophthalamide ligands (5LI-IAM-X) has been prepared (X = H, CH 3 , (C=O)NHCH 3 , SO 3 -, NO 2 , OCH 3 , F, Cl, Br) to probe the effect of substituting the isophthalamide ring on ligand and Tb(III) emission in order to establish a method for predicting the effects of chromophore modification on Tb(III) luminescence. The energies of the ligand singlet and triplet excited states are found to increase linearly with the -withdrawing ability of the substituent. The experimental results are supported by 2 time-dependent density functional theory (TD-DFT) calculations performed on model systems, which predict ligand singlet and triplet energies within ~5% of the experimental values. The quantum yield () values of the Tb(III) complex increases with the triplet energy of the ligand, which is in part due to the decreased non-radiative deactivation caused by thermal repopulation of the triplet. Together, the experimental and theoretical results serve as a predictive tool that can be used to guide the synthesis of ligands used to sensitize lanthanide luminescence.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Predicting Efficient Antenna Ligands for Tb(III) Emission

Samuel

Raymond

2008

Inorg. Chem.

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“…27 A esfera de coordenação apresentada pelo Tb 3+ (Tabela 2) possui número de coordenação 8 e pode ser descrita como antiprisma quadrado distorcido, além disso, a maioria dos compostos formados por lantanídeos e o H 2 DPA apresentam número de coordenação 9. 27,35 Outro aspecto interessante é que a condição da síntese do referido composto impõe a um dos ligantes a permanência sob a forma monoprotonada, HDPA - 44 Como conseqüência, o rendimento quântico encontrado para a rede de coordenação ∞ [Tb(DPA)(HDPA)] é de 49,8%.…”

Section: Espectroscopia De Luminescênciaunclassified

Estudos espectroscópicos e estruturais dos polímeros de coordenação 2D, ∞[Tb(DPA)(HDPA)] e ∞[Gd(DPA)(HDPA)]

Rodrigues¹,

Brito-Silva²,

Júnior³

et al. 2009

Quím. Nova

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Recebido em 2/12/07; aceito em 1/9/08; publicado na web em 2/2/09 STRUCTURAL AND SPECTROSCOPIC STUDIES OF THE 2D COORDINATION POLYMERS, ∞ [Tb(DPA)(HDPA)] AND ∞ [Gd(DPA)(HDPA)]. This paper presents the synthesis of the coordination polymers ∞ [Ln(DPA)(HDPA)] (DPA=2,6-pyridinedicarboxylate; Ln= Tb and Gd), their structural and spectroscopic properties. The structural study reveals that the ∞ [Ln(DPA) (HDPA)] has a single Ln +3 ion coordinated with two H 2 DPA ligands in tridentade coordination mode, while two others H 2 DPA establish a syn-bridge with a symmetry-related Ln 3+ , forming a two-dimensional structure. The spectroscopic studies show that ∞ [Tb(DPA)(HDPA)] compound has high quantum yield (q x ≈ 50.0%), due to the large contribution of radiative decay rate. Moreover triplet level is localized sufficiently over the emitter level 5 D 4 of theTb 3+ ion, avoiding a retrotransference process between these states.Keywords: lanthanides; coordination polymers; luminescence. introduçãoNos últimos anos um aumento significativo nas pesquisas relacionadas aos polímeros de coordenação, como uma interface entre a química sintética e a ciência de materiais, tem desempenhado papel importante na amplificação de parâmetros para predição, controle estrutural e funcional dos sólidos cristalinos. 1 Estudos nesta área promovem um amplo campo interdisciplinar em rápida e constante ascensão, com vasta abrangência para o desenvolvimento de pesquisas. Além disso, estes compostos apresentam promissoras aplicações em diversos setores industriais estratégicos, nas quais se incluem catálise, 2,3 nanotecnologia, 4 armazenamento de gases, 5,6 sistemas óptico-eletrônicos, 7 adsorção 8,9 dentre outros.A maioria dos trabalhos recém publicados é referente ao emprego de metais de transição na construção de redes de coordenação, 10-12 enquanto os sistemas com lantanídeos são muito menos estudados. [12][13][14] Os lantanídeos possuem propriedades espectroscópicas peculiares, como tempo de vida longo e bandas de emissão finas e bem definidas. 15 Esses referidos aspectos tornam os compostos com íons lantaní-deos excelentes para o uso como dispositivos moleculares conversores de luz (DMLC), 16 com possíveis aplicações em diversificadas áreas, 17 tais como dispositivos eletroluminescentes (DOELs), 18 marcadores na determinação direta de analitos orgânicos 19 e ácidos nucléicos, 20 como sondas luminescentes em imuno-diagnóstico 21 e incorporadas em matrizes sólidas para aplicações ópticas. 22 Uma série de ligantes tem sido utilizada na síntese de novos polímeros de coordenação, dentre os quais os policarboxilatos aromáticos são particularmente interessantes devido à robustez química e propriedades fotofísicas. 23 Por exemplo, o ácido 2,6-dipicolínico (H 2 DPA) tem sido amplamente empregado na síntese de compostos com lantanídeos com potenciais aplicações em imuno-ensaios. 24 Além disso, o H 2 DPA desempenha papel interessante na construção de polímeros de coordenação, pois pode funcionar como ponte entre os centros metálicos e adotar diversos modo...

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“…Other limitations of chopper wheels include the inflexible nature of the pulse regime, the inefficient use of light energy, and the risk of image-blur arising from drive motor vibration. Ultraviolet (UV) excitation (300-350 nm) is required for most lanthanide chelate fluorescent probes (18) and nitrogen lasers have found favor as a pulsed excitation source, since they emit short ( 3 ns) powerful pulses in the UV (337 nm) and are relatively inexpensive. The low repetition rate of N 2 lasers (10-60 Hz) is a significant detraction and their rapid highvoltage discharge radiates an intense electromagnetic pulse that can cause instrumentation problems.…”

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confidence: 99%

High intensity solid‐state UV source for time‐gated luminescence microscopy

2006

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Background: The unique discriminative ability of immunofluorescent probes can be severely compromised when probe emission competes against naturally occurring, intrinsically fluorescent substances (autofluorophores). Luminescence microscopes that operate in the timedomain can selectively resolve probes with long fluorescence lifetimes (s > 100 ls) against short-lived fluorescence to deliver greatly improved signal-to-noise ratio (SNR). A novel time-gated luminescence microscope design is reported that employs an ultraviolet (UV) light emitting diode (LED) to excite fluorescence from a europium chelate immunoconjugate with a long fluorescence lifetime. Methods: A commercial Zeiss epifluorescence microscope was adapted for TGL operation by fitting with a time-gated image-intensified CCD camera and a highpower (100 mW) UV LED. Capture of the luminescence was delayed for a precise interval following excitation so that autofluorescence was suppressed. Giardia cysts were labeled in situ with antibody conjugated to a europium chelate (BHHST) with a fluorescence lifetime >500 ls. Results: BHHST-labeled Giardia cysts emit at 617 nm when excited in the UV and were difficult to locate within the matrix of fluorescent algae using conventional fluorescence microscopy, and the SNR of probe to autofluorescent background was 0.51:1. However in time-gated luminescence mode with a gate-delay of 5 ls, the SNR was improved to 12.8:1, a 25-fold improvement. Conclusion: In comparison to xenon flashlamps, UV LEDs are inexpensive, easily powered, and extinguish quickly. Furthermore, the spiked emission of the LED enabled removal of spectral filters from the microscope to significantly improve efficiency of fluorescence excitation and capture. q

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Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield

Cited by 1,599 publications

References 46 publications

Predicting Efficient Antenna Ligands for Tb(III) Emission

Predicting Efficient Antenna Ligands for Tb(III) Emission

Estudos espectroscópicos e estruturais dos polímeros de coordenação 2D, ∞[Tb(DPA)(HDPA)] e ∞[Gd(DPA)(HDPA)]

High intensity solid‐state UV source for time‐gated luminescence microscopy

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