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Advances in chemical control of the photophysical properties of transition-metal complexes are revolutionizing a wide range of technologies, particularly photocatalysis and light-emitting diodes, but they rely heavily on molecules containing precious metals such as ruthenium and iridium. Although the application of earth-abundant 'early' transition metals in photosensitizers is clearly advantageous, a detailed understanding of excited states with ligand-to-metal charge transfer (LMCT) character is paramount to account for their distinct electron configurations. Here we report an air- and moisture-stable, visible light-absorbing Zr(IV) photosensitizer, Zr(PDP), where [PDP] is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. This molecule has an exceptionally long-lived triplet LMCT excited state (τ = 350 μs), featuring highly efficient photoluminescence emission (Ф = 0.45) due to thermally activated delayed fluorescence emanating from the higher-lying singlet configuration with significant LMCT contributions. Zr(PDP) engages in numerous photoredox catalytic processes and triplet energy transfer. Our investigation provides a blueprint for future photosensitizer development featuring early transition metals and excited states with significant LMCT contributions.
This article was published in the following journal.
Name: Nature chemistry
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A Randomized controlled Clinical trial including 96 patients in which aim is to investigate the clinical outcome of dental implants in titanium-zirconium alloy compared to traditional tita...
This is a multi-center, randomized study to compare blood and urine cobalt, chromium, and titanium ion levels of a metal-on-metal articular bearing coupled with two different head sizes to...
Zirconium. A rather rare metallic element, atomic number 40, atomic weight 91.22, symbol Zr. (From Dorland, 28th ed)
Neutral or negatively charged ligands bonded to metal cations or neutral atoms. The number of ligand atoms to which the metal center is directly bonded is the metal cation's coordination number, and this number is always greater than the regular valence or oxidation number of the metal. A coordination complex can be negative, neutral, or positively charged.
Measurement of the intensity and quality of fluorescence.
An analytical method for detecting and measuring FLUORESCENCE in compounds or targets such as cells, proteins, or nucleotides, or targets previously labeled with FLUORESCENCE AGENTS.
A type of FLUORESCENCE SPECTROSCOPY using two FLUORESCENT DYES with overlapping emission and absorption spectra, which is used to indicate proximity of labeled molecules. This technique is useful for studying interactions of molecules and PROTEIN FOLDING.