A Water‐Stable and Strongly Luminescent Terbium(III) Macrocyclic Complex Incorporating an Intracyclic Pyrazolylpyridine Chromophore

Photofunctionalization of a Pentamethylcyclopentadienyl Ligand with the N-Phenylcarbazolyl Group To Prepare a Highly Luminescent Tb3+ Complex Having a Fast Radiation Rate

“…The quantum yield is comparable to those for recently reported highly luminescent terbium complexes, which used macrocyclic polyamines (0.43−0.78), pyridine derivatives (0.31−0.95), 2-hydroxyisophthalamide derivatives (0.40−0.63), and others (0.40−0.85) as ligands. The lifetime (τ) of 1 in THF at room temperatue (400 μs) is considerably shorter than those found in the highly luminescent terbium complexes discussed above (∼3.16 ms) ,− and is slightly longer than that found in the organometallic terbium complex [Tb(η 5 -C 5 H 4 CH 3 ) 2 Cl(THF)] (300 μs) . Thus, the radiative rate constant ( k r = Φ/τ) of 1 is calculated to be k r = 1.68 × 10 3 s −1 , which is the highest in the terbium complexes discussed above (∼1.59 × 10 3 s −1 : mostly less than 0.90 × 10 3 s −1 ).…”

“…The luminescence quantum yield (Φ) of 1 was determined to be 0.67 in THF using 9,10-diphenylanthracene in cyclohexane as a reference (Φ = 0.97) . The quantum yield is comparable to those for recently reported highly luminescent terbium complexes, which used macrocyclic polyamines (0.43−0.78), pyridine derivatives (0.31−0.95), 2-hydroxyisophthalamide derivatives (0.40−0.63), and others (0.40−0.85) as ligands. The lifetime (τ) of 1 in THF at room temperatue (400 μs) is considerably shorter than those found in the highly luminescent terbium complexes discussed above (∼3.16 ms) ,− and is slightly longer than that found in the organometallic terbium complex [Tb(η 5 -C 5 H 4 CH 3 ) 2 Cl(THF)] (300 μs) .…”

“…To date, various photofunctionalized ligands have been developed and successfully utilized as photosensitizers for transition-metal and lanthanide complexes . Among them, macrocyclic polyamines such as cyclam (1,4,8,11-tetraazacyclotetradecane) and tacn (1,4,7-triazacyclononane), which are popular ligands in inorganic chemistry, are widely employed as useful frameworks to construct adaptable and efficient photofunctionalized ligands. , Although the anionic pentamethylcyclopentadienyl ligand (Cp* = η 5 -C 5 Me 5 ) is one of the most common and important ligands in organometallic chemistry, photofunctionalized Cp* derivatives have been hitherto unknown because of troublesome synthesis and isolation of the ligand . We believe that photofunctionalized Cp* ligands could open a new field of organometallic chemistry, including developments of novel photocatalysts and luminous materials.…”

3D Lanthanide Metal–Organic Frameworks Based on Mono-, Tri-, and Heterometallic Tetranuclear Clusters as Highly Selective and Sensitive Luminescent Sensor for Fe3+ and Cu2+ Ions

“…The intrinsic quantum yield for Tb 3+ (Φ Tb ) estimated through eq 4 is 94% on the basis of the hypothesis that the decay process at 77 K in a deuterated solvent is purely radiative. 63 τ τ Φ = / obs(298K) obs(77K)…”

Synthesis, Luminescence Properties of Eu (III) and Tb (III) Complexes with a Polyamine Polycarboxylic Ligand as well as Their Binding Characteristics with Bovine Serum Albumin (BSA)

“…They have exhibited good luminescence properties. [8][9][10][11][12] 2, 6-Dipicolinic acid (DPA) is an excellent lanthanide binding substance on the basis of the fact that carboxylic acid groups interacted strongly with the oxophilic lanthanoids, which have proved to efficiently sensitize lanthanide ion luminescence and exhibit higher luminescent stabilities than those ligated with other organic ligands. 13 Given the fascinating properties and the important potential applications of these lanthanide complexes, we were prompted to construct a new ployfunctional molecule featuring large π-conjugated system named (4, 4 -((3, 3 -(pyridine-2, 6-diyl)bis(5-phenyl-1H-pyrazole-3, 1-diyl)bis(methylene))bis (pyridine-2, 6-dicarboxylic acid L), which has multiple N and O donor atoms as coordination sites, providing a nine-coordinating environment for the Eu(III) and Tb(III) ions and reducing the possibility of coordinated water molecules involved.…”