High-Nuclearity Lanthanide–Titanium Oxo Clusters as Luminescent Molecular Thermometers with High Quantum Yields

Lu, Dong-Fei; Hong, Zi-Feng; Xie, Jing; Kong, Xiang‐Jian; Liu, Long; Zheng, Lan‐Sun

doi:10.1021/acs.inorgchem.7b01522

Cited by 62 publications

(45 citation statements)

References 62 publications

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“…Because the intensity of the Eu is independent on the local environment, the intensity ratio of these two signals can be employed to probe the local coordination environment of Eu 3+ . 28 In this case, the ratio for Eu-1 solid-state sample was determined to be around 14.8, satisfactorily matching with that from solution (i.e., ca. 14.9).…”

supporting

confidence: 60%

Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands

Subramanian

Matthews

et al. 2018

Dalton Trans.

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Polyoxotitanate (POT) cages have attracted considerable attention recently; much of this from the fact that they can be considered to be structural models for the technologically important semiconductor TiO2. Among the reported POT cages, lanthanide-containing (Ln-POT) cages are of particular interest owing to the fascinating luminescence properties of Ln3+ ions and the versatile coordination environments that they can adopt. In the present study, we report the energy transfer mechanism and photoluminescence properties of a series of isostructural Ln-POT cages coordinated by salicylate ligands, of general formula [LnTi6O3(OiPr)9(salicylate)6] (Ln-1, Ln = La to Er excluding Pm). Both visible (for Pr-1, Sm-1, Eu-1, Ho-1 and Er-1) and near-infrared (for Nd-1 and Er-1) Ln3+-centred photoluminescence can be sensitised in solution, and most importantly, their excitation bands all extend well into the visible region up to 475 nm. With the assistance of steady-state and time-resolved photoluminescence spectroscopy, an energy-transfer mechanism involving the salicylate-to-Ti4+ charge-transfer state is proposed to account for the largely red-shifted excitation wavelengths of these Ln-1 cages. The photoluminescence quantum yield of Nd-1 upon excitation via the charge-transfer state reaches 0.30 ± 0.01% in solution, making it among the highest reported values for Nd3+-complexes in the literature.

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supporting

confidence: 60%

Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands

Subramanian

Matthews

et al. 2018

Dalton Trans.

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“…Lanthanide‐transition metal (3d–4f) clusters combine 4f and 3d metal elements and have attracted widely attention because of their unique optical, electronic, magnetic and catalytic properties . In terms of catalysis, 3d–4f clusters were regarded as promising photocatalytic materials due to the synergistic effect between the 4f and 3d ions .…”

Section: Heterometallic 3d–4f Clusters (Lanthanide–transition Metal)mentioning

confidence: 99%

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

2020

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Water splitting based on first‐row transition metal (3d) photocatalysts is a cost‐effective technology for the conversion of abundant solar energy into useful energy on a large scale. The catalytic core of photosynthetic enzymes is a cubic CaMn4O5 cluster. Illuminated by natural photosynthesis, artificial solar water splitting photocatalysts composed of metal clusters are now being designed and tested. Ideally, such photocatalysts composed of atomically precise metal clusters with regular crystal structures are promising model catalysts that can be used to study structure–performance relationships. Recent advances based on metal cluster designs have improved our understanding of photoinduced charge separation and catalytic water redox reactions. This Minireview summarizes the recent advances in 3d metal cluster photocatalysts with well‐defined structures for photocatalytic water splitting and focuses on different clusters with tunable structures that are capable of achieving better photocatalytic properties.

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“…Lu et al . synthesized several europium‐titanium oxo‐clusters that exhibit these properties . The clusters were formed in a reaction with t‐butlybenzoic acid, Eu(aca) 3 , and Ti(OPr) 4 , and the structures were confirmed by X‐ray crystallography.…”

Section: Emission Intensitymentioning

confidence: 92%

Latest Trends in Temperature Sensing by Molecular Probes

et al. 2020

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In this Review, we summarize the work in the last ten years on the development of fluorescent molecular probes with possible applications in microscopic thermometry. We discuss four principal types of temperature‐dependent photoluminescence features: 1) Emission intensity; 2) Ratio of emission intensities; 3) Emission peak shift; and 4) Emission lifetime. We compare the advantages, limitations, and challenges of the different probes using these types of sensing mechanisms. By focusing on molecular probes, rather than nanoparticles or polymers, the mechanisms of temperature dependence are discussed thoroughly, with the most common including twisted intramolecular charge transfer (TICT), aggregation‐induced emission (AIE), and mechanically induced change in emission (MICE). With many different confounding variables associated with each experimental method and mechanism of temperature‐dependent photoluminescence, lanthanide and transition metal complexes seem to be promising candidates for future microscopic thermometry applications.

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High-Nuclearity Lanthanide–Titanium Oxo Clusters as Luminescent Molecular Thermometers with High Quantum Yields

Cited by 62 publications

References 62 publications

Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands

Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

Latest Trends in Temperature Sensing by Molecular Probes

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