U-type π-conjugated phosphorescent ligand sensitized lanthanide metal-organic frameworks for efficient white-light-emitting diodes.

Lanthanide metal-organic framework (Ln-MOF) based phosphors for light-emitting diodes (LEDs) play an important role in the fields of solid-state lighting and display. The rational design of organic antennae to address the drawback of low extinction coefficients of the lanthanide ions is highly desired. In this work, we provide a new design strategy to achieve an energy transfer molecule with a through-space conjugated folded structure, which can strengthen the skeleton rigidity and facilitate triplet state energy transfer. Consequently, one U-type π-conjugated molecule 2,6-bis(3,5-dicarboxylphenoxy) pyridine (H4L) was selected as a light gatherer to sensitize lanthanide ions for the construction of Ln-MOFs [Ln(HL)(H2O)3]n (Eu-MOF and Tb-MOF), which exhibit a long-lived luminescence lifetime (0.88 ms for Eu-MOF and 1.31 ms for Tb-MOF) and high quantum yields (50.87% for Eu-MOF and 85.64% for Tb-MOF). Furthermore, a white LED device with a colour rendering index (89) was fabricated using the mixture of Ln-MOFs with a commercial blue phosphor.

Fast photocatalytic degradation of rhodamine B using indium-porphyrin based cationic MOF under visible light irradiation.

A broad light-harvesting range and efficient charge separation are two main ways to enhance the visible photocatalytic performance of semiconductors. Herein, an ionic porphyrin MOF [In(TPyP)]·(NO3) (1) (TPyP = 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin) was synthesized via in situ metalation. The orderly arranged porphyrin photosensitizer and the internal electric field between the MOF host and NO3- guests enable effective visible light response and electron-hole separation. Consequently, the as-synthesized MOF shows efficient photocatalytic degradation of rhodamine B (RhB), methyl orange (MO) and methylene blue (MB) organic pollutants. It can degrade 99.07% of RhB within only 20 minutes under visible light irradiation (λ > 420 nm) with a high chemical reaction rate constant of 0.2400 min-1. The photocatalytic activity of the title MOF is more efficient than those of other reported MOFs, COFs and even inorganic semiconductors. The reusability, energy level, band gap, charge distribution and main degradation mechanisms of the photocatalyst were well studied.

Angle-Dependent Polarized Emission and Photoelectron Performance of Dye-Encapsulated Metal-Organic Framework.

Molecule-based crystalline materials with angle-dependent polarized emission have attracted considerable attention owing to their extensive applications in displays and anticounterfeiting. Herein, one anionic metal-organic framework (MOF) {[Zn2.5(µ3-OH)(NDC)2(HNDC)](HPIM)}n was constructed on the basis of an excellent photoactive ligand naphthalene-1,4-dicarboxylic acid (H2NDC). The protonated 2-propylimidazole (HPIM) guests residing in the nanochannels of MOF can be exchanged by a D-π-A cationic dye. The resulted host-guest system shows a rare example of ratiometric fluorescent polarizations and highly enhanced photoelectron performance in comparison with the pristine MOF.