Effective Photosensitization in Excited‐State Equilibrium: Brilliant Luminescence of Tb<sup>III</sup> Coordination Polymers Through Ancillary Ligand Modifications

Kitagawa, Yuichi; Moriake, Ryoma; Akama, Tomoko; Saito, Koki; Aikawa, Kota; Shoji, Sunao; Fushimi, Koji; Kobayashi, Masato; Taketsugu, Tetsuya; Hasegawa, Yasuchika

doi:10.1002/cplu.202200236

Cited by 8 publications

(9 citation statements)

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“…[ 50 ] In this regard, the architecture of the auxiliary ligands (i.e., phosphine oxide) has also a significant impact on the excited‐triplet‐state lifetimes of sensitizer ligands (hexafluoroacetylacetonato), builds a stiff coordination structure through intermolecular interactions, as well as leading to the incredible thermal stability of TbIII complexes. [ 51 ] The sensitizer ligands govern the excited state equilibrium between the TbIII and sensitizer, enabling the formation of TbIII coordination to have substantial emission (≥70%) quantum yields. To investigate the effects of the β‐diketonato and N‐oxide ligands on thermometric features, a family of homodinuclear luminous (LnIII = GdIII, EuIII) complexes were developed and examined by the presence of two nonradiative deactivation channels, ligand to metal charge transfer and back energy transfer from EuIII to the ligand triplet levels.…”

Section: Methodsmentioning

confidence: 99%

Luminescence‐Based Infrared Thermal Sensors: Comprehensive Insights

Fahad,

Li,

Zhai

et al. 2023

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Recent chronological breakthroughs in materials innovation, their fabrication, and structural designs for disparate applications have paved transformational ways to subversively digitalize infrared (IR) thermal imaging sensors from traditional to smart. The noninvasive IR thermal imaging sensors are at the cutting edge of developments, exploiting the abilities of nanomaterials to acquire arbitrary, targeted, and tunable responses suitable for integration with host materials and devices, intimately disintegrate variegated signals from the target onto depiction without any discomfort, eliminating motional artifacts and collects precise physiological and physiochemical information in natural contexts. Highlighting several typical examples from recent literature, this review article summarizes an accessible, critical, and authoritative summary of an emerging class of advancement in the modalities of nano and micro‐scale materials and devices, their fabrication designs and applications in infrared thermal sensors. Introduction is begun covering the importance of IR sensors, followed by a survey on sensing capabilities of various nano and micro structural materials, their design architects, and then culminating an overview of their diverse application swaths. The review concludes with a stimulating frontier debate on the opportunities, difficulties, and future approaches in the vibrant sector of infrared thermal imaging sensors.

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Section: Methodsmentioning

confidence: 99%

Luminescence‐Based Infrared Thermal Sensors: Comprehensive Insights

Fahad,

Li,

Zhai

et al. 2023

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“…Other reports indicate that the excited‐state equilibrium strongly depends on the T 1 lifetime. We have prepared five Tb III coordination polymers (Figure 10d) containing hexafluoroacetylacetonate (hfa, T 1 =22,100 cm −1 ) and five‐types of phosphine oxide linkers (1,4‐disubstituted benzene unit (T 1 =27,200 cm −1 ), 2,5‐disubstituted p ‐xylene unit (T 1 =24,600 cm −1 ), 1,3‐disubstituted benzene unit (T 1 =27,300 cm −1 ), 2,5‐disubstituted furan unit (T 1 =23,000 cm −1 ), and m ‐disubstituted carborane unit (T 1 =27,700 cm −1 )) [7a] . The hfa ligand shows effective reverse energy transfer (from the Tb III ion to hfa), [31b–c] and the phosphine oxide linkers strongly affected the hfa T 1 lifetime, causing a change in the excited‐state equilibrium behavior between Tb III and hfa.…”

Section: Luminescent Oxygen Sensormentioning

confidence: 99%

Luminescent Lanthanide Complexes for Effective Oxygen‐Sensing and Singlet Oxygen Generation

et al. 2023

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Oxygen quantification using luminescence has attracted considerable attention in various fields, including environmental monitoring and clinical analysis. Among the reported luminophores, trivalent lanthanide complexes have displayed characteristic narrow emission bands with high brightness. This bright emission is based on photo‐sensitized energy transfer via organic triplet states. The organic triplet states in lanthanide complexes effectively react with the triplet oxygen, enabling oxygen quantification by lanthanide luminescence. Some TbIII and EuIII complexes with slow deactivation processes have also formed the excited state equilibrium, thus resulting in the emission‐lifetime based oxygen sensing property. The combination of TbIII/EuIII emission, EuIII/SmIII emission, EuIII/ligand phosphorescence, and ligand fluorescence/ligand phosphorescence provide the ratiometric oxygen‐sensing properties. Moreover, the reaction generates singlet oxygen species which exhibit numerous applications in the photo‐medical field. The ligands with large π‐conjugated aromatic systems, such as porphyrin, phthalocyanine, and polyaromatic compounds, induces highly efficient oxygen generation. The combination of effective luminescence with singlet‐oxygen generation by the lanthanide complexes render them suitable for photo‐driven theranostics. This review summarizes the research progress of lanthanide complexes with efficient oxygen‐sensing and singlet‐oxygen generation properties.

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“…The energetic difference (ΔE) between 3 T and 5 D 0 or 5 D 4 is most significant: if the ligand triplet is less than roughly 2000 cm -1 above 5 D 0 (Malta et al, 1997) or 5 D 4 (Latva et al, 1997), energy back transfer will increasingly go at the cost of efficiency. However, if ancillary ligands with low lying triplets below the antenna are present, resonant energy back transfer may occur and can even enhance the overall quantum yield (Kitagawa et al, 2022). Additionally, non-radiative deactivation by co-coordinated, high frequency oscillators like H 2 O must be suppressed for high efficiency, which can be accomplished by the employment of ancillary ligands to avoid H 2 O-coordination.…”

Section: Complexesmentioning

confidence: 99%

High brightness red emitting polymer beads for immunoassays: Comparison between trifluoroacetylacetonates of Europium

et al. 2023

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Efficiently luminescing spherical polymer particles (beads) in the nanoscale regime of up to approximately 250 nm have become very valuable tools in bioanalytical assays. Eu3+- complexes imbedded in polymethacrylate and polystyrene in particular proved to be extraordinarily useful in sensitive immunochemical and multi-analyte assays, and histo- and cytochemistry. Their obvious advantages derive from both, the possibility to realize very high ratios of emitter complexes to target molecules, and the intrinsically long decay times of the Eu3+-complexes, which allows an almost complete discrimination against bothersome autofluorescence via time-gated measuring techniques; the narrow line emission in conjunction with large apparent Stokes shifts are additional benefits with regard to spectral separation of excitation and emission with optical filters. Last but not least, a reasonable strategy to couple the beads to the analytes is mandatory. We have thus screened a variety of complexes and ancillary ligands; the four most promising candidates evaluated and compared to each other were β-diketonates (trifluoroacetylacetonates, R-CO-CH-CO-CF3, R = - thienyl, -phenyl, -naphthyl and -phenanthryl); highest solubilities in polystyrene were obtained with trioctylphosphine co-ligands. All beads had overall quantum yields in excess of 80% as dried powders and lifetimes well beyond 600 µs. Core-shell particles were devised for the conjugation to model proteins (Avidine, Neutravidine). Their applicability was tested in biotinylated titer plates using time gated measurements and a Lateral Flow Assay as practical examples.

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Effective Photosensitization in Excited‐State Equilibrium: Brilliant Luminescence of Tb^III Coordination Polymers Through Ancillary Ligand Modifications

Cited by 8 publications

References 2 publications

Luminescence‐Based Infrared Thermal Sensors: Comprehensive Insights

Luminescence‐Based Infrared Thermal Sensors: Comprehensive Insights

Luminescent Lanthanide Complexes for Effective Oxygen‐Sensing and Singlet Oxygen Generation

High brightness red emitting polymer beads for immunoassays: Comparison between trifluoroacetylacetonates of Europium

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Effective Photosensitization in Excited‐State Equilibrium: Brilliant Luminescence of TbIII Coordination Polymers Through Ancillary Ligand Modifications

Cited by 8 publications

References 2 publications

Luminescence‐Based Infrared Thermal Sensors: Comprehensive Insights

Luminescence‐Based Infrared Thermal Sensors: Comprehensive Insights

Luminescent Lanthanide Complexes for Effective Oxygen‐Sensing and Singlet Oxygen Generation

High brightness red emitting polymer beads for immunoassays: Comparison between trifluoroacetylacetonates of Europium

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Effective Photosensitization in Excited‐State Equilibrium: Brilliant Luminescence of Tb^III Coordination Polymers Through Ancillary Ligand Modifications