Highly Stable Europium(III) Tetrahedral (Eu4L4)(phen)4 Cage: Structure, Luminescence Properties, and Cellular Imaging.

Luminescent lanthanide cages have many potential applications in guest recognition, sensing, magnetic resonance imaging (MRI), and bioimaging. However, these polynuclear lanthanide assemblies' poor stability, dispersity, and luminescence properties have significantly constrained their practical applications. Furthermore, it is still a huge challenge to simultaneously synthesize and design lanthanide organic polyhedra with high stability and quantum yield. Herein, we demonstrate a simple and robust strategy to improve the rigidity, chemical stability, and luminescence of an Eu(III) tetrahedral cage by introducing the conjugated planar auxiliary phen ligand. The self-assembled tetrahedral cage, (Eu4L4)(phen)4 [L = (4,4',4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine), phen = 1,10-phenanthroline], exhibited characteristic luminescence of Eu3+ ions with high quantum yield (41%) and long lifetime (131 µs) in toluene (1.0 × 10-6 M). Moreover, the Eu(III) cage was stable in water and even in an aqueous solution with a pH range of 1-14. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and cellular imaging revealed that the Pluronic F127-coated hybrid material, (Eu4L4)(phen)4@F127, exhibited low cytotoxicity, good biocompatibility, and cellular imaging ability, which may inspire more insights into the development of lanthanide organic polyhedra (LOPs) for potential biomedical applications.

Mechanically Robust, Durable, and Multifunctional Hyper-Crosslinked Elastomer Based on Metal-Organic-Cluster Crosslinker: The Role of Topological Structure.

Polymer materials formed by conventional metal-ligand bonds have very low branch functionality, the crosslinker of such polymer usually consists of 2-4 polymer chains and a single metal ion. Thus, these materials are weak, soft, humidity-sensitive, and unable to withstand their shape under long-term service. In this work, a new hyperbranched metal-organic cluster (MOC) crosslinker containing up to 16 vinyl groups is prepared by a straightforward coordination reaction. Compared with the current typical synthesis of metal-organic cages (MOCs) or metal-organic-polyhedra (MOP) crosslinkers with complex operations and low yield, the preparation of the MOC is simple and gram-scale. Thus, MOC can serve as a high-connectivity crosslinker to construct hyper-crosslinked polymer networks. The as-prepared elastomer exhibits mechanical robustness, creep-resistance, and humidity-stability. Besides, the elastomer possesses self-healing and recyclability at mild condition as well as fluorescence stability. These impressive comprehensive properties are proven to originate from the hyper-crosslinked topological structure and microphase-separated morphology. The MOC-driven hyper-crosslinked elastomers provide a new solution for the construction of mechanically robust, durable, and multifunctional polymers.

Methyl 2-hydr-oxy-3-nitro-benzoate.

The title compound, C(8)H(7)NO(5), assumes an approximately planar mol-ecular structure with an intra-molecular O-H⋯O hydrogen bond between the hydr-oxy and carboxyl-ate groups. Weak inter-molecular C-H⋯O hydrogen bonding is present in the crystal structure.

Preparation, Structure, Photoluminescent and Semiconductive Properties, and Theoretical Calculation of a Mononuclear Nickel Complex with 3-Hydroxy-2- Methylquinoline-4-Carboxylato Ligand.

A novel nickel complex with mixed ligands [Ni(L)2(EtOH)2(MeOH)2] (HL = 3-hydroxy-2-methylquinoline-4-carboxylic acid) has been synthesized through solvothermal reaction and its crystal structure was determined by single-crystal X-ray diffraction technique. Single-crystal X-ray diffraction analyses reveals that the title compound crystallizes in the triclinic system of the P-1 space group, and exists as isolated mononuclear complex. The intermolecular hydrogen bonds lead to the formation of chains, and the layered supramolecular structure is formed by the strong ααααα stacking interactions. Solid-state photoluminescent characterization reveals that the title compound has an emission in the green region. Time-dependent density functional theory (TDDFT) calculation shows that the nature of the photoluminescence of the title compound originates from the ligand-to-ligand charge transfer (LLCT; from the HOMO of the p-orbital of ligand HMCA to the LUMO of the oxygen atoms). A wide optical band gap of 2.25 eV is found by the solid-state UV/vis diffuse reflectance spectrum.

[Preparation and photoluminescence study of Er3+ : Y2O3 transparent ceramics].

Y2O3 acted as the matrix material, which was doped with different concentrations of Er3+, Er3+ : Y2O3 nanocrystalline powder was prepared by co-precipitation method, and Er3+ : Y2O3 transparent ceramics was fabricated by vacuum sintering at 1700 degrees C, 1 x 10(-3) Pa for 8 h. By using the X-ray diffraction (D/MAX-RB), transmission electron microscopy(Philips EM420), automatic logging spectrophotometer(DMR-22), fluorescence analyzer (F-4500) and 980 nm diode laser, the structural, morphological and luminescence properties of the sample were investigated. The results show that Er3+ dissolved completely in the Y2O3 cubic phase, the precursor was amorphous, weak diffraction peaks appeared after calcination at 400 degrees C, and if calcined at 700 degrees C, the precursor turned to pure cubic phase. With increasing the calcining temperature, the diffraction peaks became sharp quickly, and when the calcining temperature reached 1100 degrees C, the diffraction peaks became very sharp, indicating that the grains were very large. The particles of Er+ : Y2O3 is homogeneous and nearly spherical, the average diameter of the particles is in the range of 40-60 nm after being calcined at 1000 degrees C for 2 h. The relative density of Er3+ : Y2O3 transparent ceramics is 99.8%, the transmittance of the Er2+ : Y2O3 transparent ceramics is markedly lower than the single crystal at the short wavelength, but the transmittance is improved noticeably with increasing the wavelength, and the transmittance exceeds 60% at the wavelength of 1200 nm. Excited under the 980 nm diode laser, there are two main up-conversion emission bands, green emission centers at 562 nm and red emission centers at 660 nm, which correspond to (4)S(3/2) / (2)H(11/2) - (4)I(15/2) and (4)F(9/2) - (4)I(15/2) radiative transitions respectively. By changing the doping concentrations of Er3+, the color of up-conversion luminescence can be tuned from green to red gradually. The luminescence intensity is not reinforce with the increase in the concentration, so the doping concentration of Er3+ should not exceed 2%. If the doping concentration of Er3+ exceeds the range, the concentration has very small effect on the improvement of luminescence intensity.

2-[(2H-Tetra-zol-2-yl)meth-yl]benzonitrile.

The title compound, C(9)H(7)N(5), is non-planar with a dihedral angle between the substituted benzene and tetra-zole rings of 71.13 (9)°. Molecules are connected in centrosymmetric dimers by weak C-H⋯N inter-actions [C⋯N is 3.548 (5) Å]; these are the only interactions of significance in the crystal structure.