Unraveling the Position Effect of Spiroxanthene-Based n-Type Hosts for High-Performance TADF-OLEDs.

For developing high-performance organic light-emitting diodes (OLEDs) with thermally activated delayed fluorescent (TADF) emitters, the diphenyltriazine (TRZ) unit was introduced onto the 2'- and 3'-positions of xanthene moiety of spiro[fluorene-9,9'-xanthene] (SFX) to construct n-type host molecules, namely 2'-TRZSFX and 3'-TRZSFX. The outward extension of the TRZ unit, induced by the meta-linkage, resulted in a higher planarity between the TRZ unit and xanthene moiety in the corresponding 3'-TRZSFX. Additionally, this extension led to a perched T1 level, as well as a lower unoccupied molecular orbital (LUMO) level when compared with 2'-TRZSFX. Meanwhile, the 3'-TRZSFX molecules in the crystalline state presented coherent packing along with the interaction between TRZ units; the similar packing motif was spaced apart from xanthene moieties in the 2'-TRZSFX crystal. These endowed 3'-TRZSFX superior electron transport capacity in single-carrier devices relative to the 2'-TRZSFX-based device. Hence, the 3'-TRZSFX-based TADF-OLED showed remarkable electroluminescent (EL) performance under the operating luminance from turn-on to ca. 1000 cd·m-2 with a maximum external quantum efficiency (EQEmax) of 23.0%, thanks to its matched LUMO level with 4CzIPN emitter and better electron transport capacity. Interestingly, the 2'-TRZSFX-based device, with an EQEmax of 18.8%, possessed relatively low roll-off and higher efficiency when the operating luminance exceeded 1000 cd·m-2, which was attributed to the more balanced carrier transport under high operating voltage. These results were elucidated by the analysis of single-crystal structures and the measurements of single-carrier devices, combined with EL performance. The revealed position effect of the TRZ unit on xanthene moiety provides a more informed strategy to develop SFX-based hosts for highly efficient TADF-OLEDs.

Synthesis and Properties of a Bay-Annulated-Indigo Tetramer Based on Low-Cost Spiro[Fluorene-9,9'-Xanthene] Core.

A three-dimensional bay-annulated-indigo (BAI) tetramer has been prepared by appending BAI units onto a low-cost spiro[fluorene-9,9'-xanthene] (SFX) core. The target compound 4BAI-SFX exhibits strong and broad absorption in the visible region covering the range of 450~700 nm. The electrochemical measurement illuminates the characteristics of a deep lowest unoccupied molecular orbital (LUMO) level and multiple redox states of 4BAI-SFX. These results suggest that 4BAI-SFX should be a selectable electron-transporting material for eco-friendly organic semiconductors.

Visible-Light-Promoted [5 + 1] Annulation Initiated by Electron-Donor-Acceptor Complexes: Synthesis of Perfluoroalkyl- s-Triazines.

A visible-light-promoted electron-donor-acceptor (EDA) complex-initiated [5 + 1] annulation between biguanides and perfluoroalkyl halides for the construction of perfluoroalkyl- s-triazines has been developed. It was found that both visible light and dioxygen in the air are favorable for the reaction. A radical-polar crossover mechanism was proposed, in which sequential SET, radical combination, HF elimination, electrocyclization, and aromatization are involved.

Stable Luminous Nanocomposites of Confined Mn2+-Doped Lead Halide Perovskite Nanocrystals in Mesoporous Silica Nanospheres as Orange Fluorophores.

Creating highly stable inorganic perovskite nanocrystals (CsPbX3, where X = Cl, Br, and I) with excellent optical performance is challenging because their optical properties depend on their ionic structure and its inherent defects. Here, we present a facile and effective synthesis using a nanoconfinement strategy to grow Mn2+-doped CsPbCl3 nanocrystals embedded in dendritic mesoporous silica nanospheres (MSNs). The resulting nanocomposite is abbreviated as Cs(Pb x/Mn1- x)Cl3@MSNs and can serve as the orange emitter for white light-emitting diodes (WLEDs). The MSN matrix was prepared via a templated sol-gel technique as monodispersed center-radial dendritic porous particles, with a diamater of ∼105 nm and an inner pore size of ∼13 nm. The MSN was then utilized as the matrix to initiate the growth of Mn-doped perovskite nanocrystals (NCs). The NCs in the resulting composite have an average diameter of 8 nm and a photoluminescence quantum yield of >30%. In addition, the optical properties of the Cs(Pb x/Mn1- x)Cl3@MSNs can be tuned by varying the Mn2+ doping level. The resulting composites presented a significantly improved resistance to ultraviolet (UV) light, temperature, and moisture compared to that of bare Cs(Pb0.72/Mn0.28)Cl3. Finally, we fabricated down-converting WLEDs by using Cs(Pb x/Mn1- x)Cl3@MSNs as the orange-emitting phosphor deposited onto UV-emitting chips, demonstrating their promising applications in solid-state lighting. This work provides a valuable approach to fabricating stable orange luminophores as replacements for traditional emitters in light-emitting diode devices.

Tailoring the structure, pH sensitivity and catalytic performance in Suzuki-Miyaura cross-couplings of Ln/Pd MOFs based on the 1,1'-di(p-carboxybenzyl)-2,2'-diimidazole linker.

An array of heterobimetallic Pd/Ln MOFs (1-4) with Sm, Eu, Tb, Dy as preferred metal nodes and 1,1'-di(p-carboxybenzyl)-2,2'-diimidazole (H2L) as a fairly suitable bifunctional organic linker have been synthesized, fully characterized and tested as catalysts in cross-coupling reactions. These robust MOFs, ensuring a uniform distribution of Pd, showed excellent stability in air and high catalytic activity in Suzuki-Miyaura reactions conducted in neat water, neat ethanol as well as water-ethanol mixture. Depending on the solvent, complex 1 could be effectively recycled 4-8 times without significant loss of catalytic activity. Importantly, this complex was found to be pH responsive in a reversible way, enabling convenient recovery from acidic aqueous solutions, indicating good recyclability as well as environment-friendly separation of the metal residues after the reaction.

t-BuONa-mediated direct C-H halogenation of electron-deficient (hetero)arenes.

An efficient halogenation of electron-deficient (hetero)arenes is described. The reaction utilizes common t-BuONa as a catalyst (for iodination) or a promoter (for bromination and chlorination), and perfluorobutyl iodide, CBr4 or CCl4 as the readily-available halogenating agents, respectively. The protocol features broad scope, high efficiency, mild conditions and gram scalability. An ionic pathway involving halogen bond formation and halophilic attack is proposed. The utility of the resulting iodinated heteroarenes is demonstrated in visible light-mediated Caryl-Caryl cross-coupling reaction.

Nanorod Suprastructures from a Ternary Graphene Oxide-Polymer-CsPbX3 Perovskite Nanocrystal Composite That Display High Environmental Stability.

Despite the exceptional optoelectronic characteristics of the emergent perovskite nanocrystals, the ionic nature greatly limits their stability, and thus restricts their potential applications. Here we have adapted a self-assembly strategy to access a rarely reported nanorod suprastructure that provide excellent encapsulation of perovskite nanocrystals by polymer-grafted graphene oxide layers. Polyacrylic acid-grafted graphene oxide (GO-g-PAA) was used as a surface ligand during the synthesis of the CsPbX3 perovskite nanocrystals (NCs), yielding particles (5-12 nm) with tunable halide compositions that were homogeneously embedded in the GO-g-PAA matrix. The resulting NC-GO-g-PAA exhibits a higher photoluminescence quantum yield than previously reported encapsulated NCs while maintaining an easily tunable bandgap, allowing for emission spanning the visible spectrum. The NC-GO-g-PAA hybrid further self-assembles into well-defined nanorods upon solvent treatment. The resulting nanorod morphology imparts extraordinary chemical stability toward protic solvents such as methanol and water and much enhanced thermal stability. The introduction of barrier layers by embedding the perovskite NCs in the GO-g-PAA matrix, together with its unique assembly into nanorods, provides a novel strategy to afford robust perovskite emissive materials with environmental stability that may meet or exceed the requirement for optoelectronic applications.

A Yellow-Emitting Homoleptic Iridium(III) Complex Constructed from a Multifunctional Spiro Ligand for Highly Efficient Phosphorescent Organic Light-Emitting Diodes.

To suppress concentration quenching and to improve charge-carrier injection/transport in the emission layer (EML) of phosphorescent organic light-emitting diodes (PhOLEDs), a facial homoleptic iridium(III) complex emitter with amorphous characteristics was designed and prepared in one step from a multifunctional spiro ligand containing spiro[fluorene-9,9'-xanthene] (SFX) unit. Single-crystal X-ray analysis of the resulting fac-Ir(SFXpy)3 complex revealed an enlarged Ir···Ir distance and negligible intermolecular π-π interactions between the spiro ligands. The emitter exhibits yellow emission and almost equal energy levels compared to the commercial phosphor iridium(III) bis(4-phenylthieno[3,2-c]pyridinato-N,C2')acetylacetonate (PO-01). Dry-processed devices using a common host, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl, and the fac-Ir(SFXpy)3 emitter at a doping concentration of 15 wt % exhibited a peak performance of 46.2 cd A-1, 36.3 lm W-1, and 12.1% for the current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE), respectively. Compared to control devices using PO-01 as the dopant, the fac-Ir(SFXpy)3-based devices remained superior in the doping range between 8 and 15 wt %. The current densities went up with increasing doping concentration at the same driving voltage, while the roll-offs remain relatively low even at high doping levels. The superior performance of the new emitter-based devices was ascribed to key roles of the spiro ligand for suppressing aggregation and assisting charge-carrier injection/transport. Benefiting from the amorphous stability of the emitter, the wet-processed device also exhibited respectful CE, PE, and EQE of 32.2 cd A-1, 22.1 lm W-1, and 11.3%, respectively, while the EQE roll-off was as low as 1.7% at the luminance of 1000 cd m-2. The three-dimensional geometry and binary-conjugation features render SFX the ideal multifunctional module for suppressing concentration quenching, facilitating charge-carrier injection/transport, and improving the amorphous stability of iridium(III)-based phosphorescent emitters.

The synergistic effect of cobalt on a Pd/Co catalyzed Suzuki-Miyaura cross-coupling in water.

This work introduces the new trimetallic complex CoPd2(HBPDC)2Cl4·(H2O)4(H2BPDC = 2,2'-bipyridine-4,4'-dicarboxylic acid) as a highly efficient and more cost-effective catalyst for a Suzuki-Miyaura reaction proceeding in water, without additives and under aerobic conditions. Catalytic studies revealed a synergistic Co-Pd cooperativity, fostered by ligation through H2BPDC, and accounting for the superior performance of the heterobimetallic complex vs. its Co-free counterpart.

Novel mononuclear Pt2+ and Pd2+ complexes containing (2,3-f)pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid as a multi-donor ligand. Synthesis, structure, interaction with DNA, in vitro cytotoxicity, and apoptosis.

New cytotoxic, mononuclear Pt and Pd coordination complexes featuring the planar, multi-donor ligand (2,3-f)pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid (H2PPDA) have been synthesized under hydrothermal conditions (in water, at high temperature and pressure) and fully characterized. The complexes were proven to be isostructural by applying the single-crystal X-ray diffraction technique. UV-Vis and fluorescence spectroscopy investigations on their interaction with fish sperm DNA revealed a considerable binding capacity while gel electrophoresis provided evidence in favor of cleavage of pBR322 plasmid DNA. The newly synthesized complexes manifested significant in vitro cytotoxic activity against two different human cancer cell lines, the KB and JEKO cells, with cell death mainly caused by apoptosis.

Synthesis, structure and properties of 2D lanthanide coordination polymers based on N-heterocyclic arylpolycarboxylate ligands.

The reaction of 3-(2,4-dicarboxyphenyl)-2,6-pyridinedicarboxylic acid (H4dppd) with rare earth nitrates under hydrothermal conditions generated a series of new two-dimensional (2D) coordination polymers, namely {[La(Hdppd)(H2O)2·(H2O)2]n (1), [Ln2(Hdppd)2(H2O)4·(H2O)3]n [Ln = Sm (2), Eu (3)] and [Ln(Hdppd)(H2O)3·H2O]n [Ln = Gd (4), Tb (5), Dy (6), Ho (7), Er (8)] [Hdppd = 3-(2,4-dicarboxyphenyl)-2,6-pyridinedicarboxylic trivalent anion]}. The complexes were characterized by X-ray single-crystal diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Luminescence spectroscopy of 3 and 5 showed bright red and green luminescences due to the 4f(n)-4f(n) transitions in Eu(3+) and Tb(3+) respectively, although the luminescence lifetime is shortened by non-radiative decay due to the presence of coordinating water molecules. The magnetic properties of 2-8 were measured and discussed. Compound 6 exhibits frequency dependent out-of-phase signals, and ferromagnetic coupling exists in 8.

Solvent-regulated assemblies of 1D lanthanide coordination polymers with the tricarboxylate ligand.

Solvothermal reactions of the tricarboxylic acid ligand, biphenyl-3,3',5-tricarboxylic acid (H3bpta), and rare earth nitrate (Ln(NO3)3·6H2O) in the presence of KOH or DMF produced eight 1D linear coordination polymers, namely, [La(bpta)(H2O)5·(H2O)3]n (), [Pr(bpta)(H2O)5·(H2O)2.5]n (), [Nd(bpta)(H2O)5·(H2O)1.75]n (), [Sm(bpta)(H2O)5·(H2O)0.5]n () and [Ln(bpta)(DMF)(H2O)3·(H2O)]n [Ln = Eu (), Gd (), Tb (), Dy ()]. The 1D chain further assembles into a 3D supramolecular network structure through hydrogen bonds and π-π stacking among chains. Complexes and display the typical emission spectra for lanthanide-centred luminescence. The optical properties of were analysed in detail and coincide well with the structural properties. The influence of temperature on the luminescence lifetime of has been studied and different non-radiative decay paths have been discussed. The magnetic properties show that and exhibit strong spin-orbit coupling, while weak antiferromagnetic coupling exists in .

Facile synthesis and luminescence properties of Y2O3:Ln(3+) (Ln(3+) = Eu(3+), Tb(3+), Dy(3+), Sm(3+), Er(3+), Ho(3+), Tm(3+), Yb(3+)/Er(3+), Yb(3+)/Tm(3+), Yb(3+)/Ho(3+)) microspheres.

Multicolor and monodisperse Y2O3:Ln(3+) (Ln(3+) = Eu(3+), Tb(3+), Dy(3+), Sm(3+), Er(3+), Ho(3+), Tm(3+), Yb(3+)/Er(3+), Yb(3+)/Ho(3+)) microspheres were prepared through a facile urea-assisted homogeneous precipitation method followed by a subsequent calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectrum (EDS), Fourier transformed infrared (FT-IR), thermogravimetric analysis (TGA), photoluminescence (PL) and cathodoluminescence (CL) spectra were employed to characterize the samples. The XRD results reveal that the as-prepared spheres can be well indexed to cubic Y2O3 phase with high purity. The SEM and TEM images show the obtained Y2O3:Ln(3+) samples consist of regular nanospheres with the mean diameter of 350 nm. And the possible formation mechanism is also proposed. Upon ultraviolet and low-voltage electron beams excitation, Y2O3:Ln(3+) (Ln(3+) = Eu(3+), Tb(3+), Dy(3+), Sm(3+), Er(3+), Ho(3+), Tm(3+)) samples exhibit respective bright red (Eu(3+), (5)D0 --> (7)F2), green (Tb(3+), (5)D4 --> (7)F5), blue (Dy(3+), (4)F9/2 --> (6)H13/2), yellow (Sm(3+), (4)G5/2 --> (6)H7/2), green (Er(3+), (4)S3/2 --> (4)I15/2), green (Ho(3+), (5)S2 --> (5)I8), blue (Tm(3+), (1)D2 --> (3)F4) down-conversion (DC) emissions. Under 980 nm NIR irradiation, Y2O3:Ln(3+) (Ln(3+) = Yb(3+)/Er(3+), Yb(3+)/Tm(3+) and Yb(3+)/Ho(3+)) exhibit characteristic up-conversion (UC) emissions of green (Er(3+), (2)H11/2, (4)S3/2, (2)H11/2 --> (4)I5/2), blue (Tm(3+), (1)G4 --> (3)H6) and green (Ho(3+), (5)F4, (5)S2 --> (5)I8), respectively. These merits of multicolor emissions in the visible region endow this kind of material with potential applications in the field of light display systems, lasers, and optoelectronic devices.