Tuning luminescent property of trivalent europium complex nanocrystals with fluorinated anionic ligands.

Realizing External Quantum Efficiency over 25% with Low Efficiency Roll-Off in Polymer-Based Light-Emitting Diodes Synergistically Utilizing Intramolecular Sensitization and Bipolar Thermally Activated Delayed Fluorescence Monomer

Application of the collision-complex model to the photophysical processes of singlet oxygen in liquids

Theoretical study on the neutral and ionic Cu(I) phosphorescent complexes with 2-(2′-quinolyl)benzimidazole and phosphine mixed ligand

Bright red-emitting phosphors with high color purity and high photoluminescence quantum yield (PLQY) are highly demanded for the fabrication of high-performance warm-white light-emitting diodes (LEDs). Herein, we demonstrated a novel efficient Eu3+-activated Ca2LaHf2Al3O12 garnet phosphor with excellent luminescence properties for near-ultraviolet (near-UV) excited warm-white LEDs. The Ca2LaHf2Al3O12:Eu3+ phosphors exhibited an intense excitation spectrum in the near-UV region with a maximum around 394 nm, and they produced dazzling red luminescence peaking at 592, 614, 659, and 711 nm due to the 5D0 → 7FJ (J = 1-4) transitions of Eu3+ ions when the excitation wavelength was set at 394 nm. Luminescent properties have been studied as a function of Eu3+ doping concentration, and the highest emission intensity was achieved at 50 mol % Eu3+, while the dipole-dipole interaction brought the concentration quenching effect. The Ca2LaHf2Al3O12:50%Eu3+ sample exhibited CIE chromaticity coordinates of (0.6419, 0.3575) with a color purity of 92.7%, and its PLQY was measured to be 64%. The thermal stability and activation energy of Ca2LaHf2Al3O12:50%Eu3+ phosphors were also discussed and analyzed. Finally, we made a near-UV chip-based white LED device in which the Ca2LaHf2Al3O12:50%Eu3+ phosphor was utilized as a red ingredient. A bright warm-white light emission was realized from this LED device under 80 mA driving current, accompanied by a high color rendering index (CRI) of 88.3, a low correlation color temperature of 3853 K, and good CIE chromaticity coordinates of (0.3909, 0.3934). These results revealed that these red-emitting Ca2LaHf2Al3O12:Eu3+ phosphors have promising application prospect in near-UV-excited warm-white LEDs with high a CRI.

The chelate phosphine oxide ligand bis(2-(diphenylphosphino)phenyl) ether oxide (DPEPO) was used as a unit neutral ligand to prepare the complex Eu(TTA)(3)(DPEPO) 1 (TTA = 2-thenoyltrifluoroacetonate). Compound 1 has a photoluminescence (PL) quantum yield of 55.3%, which is more than the twice of the PL quantum yield of Eu(TTA)(3)(TPPO)(2) (TPPO = triphenylphosphine oxide). Investigation indicated that DPEPO in 1 has the mezzo first triplet excited energy level (T(1)) between the first singlet excited energy level (S(1)) and T(1) of TTA, which may support one more additional energy transfer routines from the T(1) energy level of DPEPO to that of TTA, and consequently results in the improvement of energy transfer in the Eu(III) complex. DPEPO forms a complex with a more rigid and compact structure that can improve energy transfer between ligands and the center Eu(III) ion, support the higher saturation level by the coordinating ability of the oxygen atom in the ether moiety, and consequently enhance the PL intensity and efficiency of the corresponding Eu(III) complex. The multilayered electroluminescent (EL) device of 1 used as the red dopant exhibited an impressive brightness of 632 cd m(-2) at 25 V. The device had the excellent voltage-independent spectral stability with an emission peak at 615 nm. To the best of our knowledge, this luminescence is the brightest emission among Eu complexes with phosphine oxide ligands. The maximum external quantum yield (eta(ext)) of 2.89% and the maximum current and power efficiency of 4.58 cd A(-1) and 2.05 lm W(-1) were achieved at a low turn-on voltage of 7 V and current density of 0.021 mA cm(-2). These properties demonstrate that the chelate phosphine oxides ligand DPEPO can not only be favorable to form the rigid and compact complex structure and increase the efficiency of devices, but also reduce the ability of the formation of exciplex. DPEPO shows much better performance compared with the ordinary phosphine oxide ligand triphenylphosphine oxide.

Many phenomena in nature consist of multiple elementary processes. If we can predict all the rate constants of respective processes quantitatively, we can comprehensively predict and understand various phenomena. Here, we report that it is possible to quantitatively predict all related rate constants and quantum yields without conducting experiments, using multiple-resonance thermally activated delayed fluorescence (MR–TADF) as an example. MR–TADFs are excellent emitters because of its narrow emission, high luminescence efficiency, and chemical stability, but they have one drawback: slow reverse intersystem crossing (RISC), leading to efficiency roll-off and reduced device lifetime. Here, we show a quantum chemical calculation method for quantitatively obtaining all the rate constants and quantum yields. This study reveals a strategy to improve RISC without compromising other important factors: radiative decay rate constants, photoluminescence quantum yields, and emission linewidths. Our method can be applied in a wide range of research fields, providing comprehensive understanding of the mechanism including the time evolution of excitons.

Triplet energies, singlet state properties and singlet oxygen quenching rate constants and quantum yields for two cyan azamethine dyes

Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied toward the development of luminescent materials. However, previous studies have mainly focused on CT transitions between d- and π-orbitals. Herein, we report the demonstration of CT emission from 4f- to π-orbitals using a trivalent europium (Eu(III)) complex, supported by both experimental and theoretical analyses. The Eu(III) complex exhibits an eight-coordination structure, comprising three anionic nitrates and two neutral electron-donating ligands containing a carbazole unit. The diffuse reflectance spectrum of the complex displays an absorption band at 440 nm and time-resolved emission analyses reveal a characteristic emission band at 550 nm. Comparative studies employing a trivalent gadolinium (Gd(III)) complex, alongside quantum chemical analyses, confirm that the observed absorption and emission bands are associated with CT transitions between π- and 4f-orbitals. The observation of CT emission based on the 4f-orbital offers novel insights into the field of molecular luminescence science and technology.

Review: 119 refs.

Luminescence properties and crystal structure of europium complexes with phenoxyacetic acid and 2,4,6-tri(2-pyridyl)-s-triazine

Luminescence properties of some platinum (II) complexes. Counter-ion and molecular geometry effects

Eu(iii) complexes emit red light with a high color purity and have consequently attracted attention for development toward display and physical sensing applications. The characteristic pure color emission originates from the intra-4f–4f transition, and the brightness strongly depends on the electronic and steric structures of organic ligands. A large π-conjugated ligand design with a large absorption coefficient has been actively studied for achieving bright emission. The π-conjugated Eu(iii) luminophores also provide oxygen and temperature sensing properties by controlling their excited state dynamics based on π-electron systems. A comprehensive understanding of the design strategy of large π-conjugated ligands is crucial for the further development of luminescent Eu(iii) complexes. In this review, we summarize the research progress on π-conjugated Eu(iii) luminophores exhibiting bright emission and their physical sensing applications.

Probing the nature of the Co(III) ion in cobalamins: The reactions of aquacobalamin (vitamin B12a), aqua-10-chlorocobalamin and aqua-10-bromocobalamin with anionic and neutral ligands

Syntheses, structures and catecholase activity of two cobalt(III) complexes derived from N,N′-ethylenebis(3-ethoxysalicylaldiimine): A special host–guest system from a special ligand

The authors report the synthesis and luminescence properties of Ir(phen){sub 3}{sup 3+} and Ir(terp){sub 2}{sup 3+} (phen = 1,10-phenanthroline and terp = 2,6-bis(2-pyridyl)pyridine). Their emissions are assigned to predominantly {pi}-{pi}* phosphorescences. A novel excited-state complex is proposed to form between Ir(phen){sub 3}{sup 3+} and Ir(terp){sub 2}{sup 3+} and HgCl{sub 2}. Although HgCl{sub 2} is normally a quencher, it can greatly enhance the lifetimes and luminescence efficiencies of the Ir(phen){sub 3}{sup 3+} and Ir(terp){sub 2}{sup 3+} - up to an order of magnitude. The changes arise from alteration of the radiative and nonradiative rate constants in the excited-state complex. The effect of temperature, solvent, oxygen, and inert ions on the interactions of HgCl{sub 2} with the excited complexes is explored. A simple associative model accurately reproduces all lifetime and intensity changes. A rationale based on the well-known affinity of HgCl{sub 2} for aromatic molecules is proposed.