| Around the research focus of luminescent lanthanide metal-organic frameworks (Ln-MOFs) in this contribution, four types of Ln-MOFs were designed and synthesized based on aromatic carboxylic acid ligands2,2’,3,3’-H2BPDC (2,2’-Bipyridine-3,3’-dicarboxylic acid),1,4-H2BDC (1,4-Benzenedicarboxylic acid)、4,4’-H2BPDCA (4,4’-Biphenyldicarboxylicacid) and H2FDA (2,5-Furandicarboxylic acid) under hydrothermal/solvothermal conditions and their luminescent properties were mainly investigated, especially as luminescent sensors for organic small-molecules, metal cations and inorganic anions. The main research contents are carried out as following:1. A family of novel isostructural pure Ln-MOFs1-4and mixed Ln-MOFs5-9have been obtained through a mixed ligand approach using2,2’,3,3’-H2BPDC and1,4-H2BDC under hydrothermal conditions. This three-dimensional framework is constructed through Ln2binuclear cores and ligands and possesses tfz-d topology with the short (Schla fli) vertex symbol{43}2{46·618·84}. Luminescent studies illustrate that Ln-MOFs1,2, and5display highly sensitive sensing of environmental pollutants fluoride anions and organic small-molecule solvents, especially formaldehyde, acetonitrile, and acetone.2. A series of isostructural3D cationic Ln-MOFs10-15based on cubane-shaped [Ln4(μ3-OH)4]8+clusters were successfully obtained under solvothermal condition based on two types of ligands2,2’,3,3’-H2BPDC and4,4’-H2BPDCA. Luminescent studies illustrate that Ln-MOF10could be an efficient multifunctional luminescent material for high-sensitivity sensing of small organic molecules, metal cations, and anions, especially for benzene and acetone, Cu2+, and CrO42". Eu@Tb-MOFs12-15can detect quickly and efficiently the mixtures of methanol (MeOH) and ethanol (EtOH) in a wide content range. As an expected linear luminescent sensor of mixed MeOH and EtOH, Eu@Tb-MOFs15based on two emissions of Tb3+at547nm and Eu3+at618nm is not only reliable and instantaneous but also has high-sensitive sensing of the mixture of EtOH and MeOH. In simulated mixed industrial MeOH and EtOH, Eu@Tb-MOFs15also displays a high-sensitive luminescent recognition.3. A series of pure and mixed Ln-MOF16-29based on ligand H2FDA were synthesized and structurally characterized within1D lanthanide chains. By adjusting the molar ratio of Eu3+and Tb3+ions in singular mixed Ln-MOFs, their luminescent colors change from green, light green (Ln-MOF21), yellow-green (Ln-MOF23), yellow (Ln-MOF24), orange (Ln-MOF26), orange-red (Ln-MOF28), to red. Luminescent studies indicate that Ln-MOFs16,17and25can be highly sensitive to trace of phenylcarbinol in aromatic groups with super-low limit of detection10-13M and short response time20s. The relative luminescent intensities in Ln-MOFs16and17can be linearly fitted with the concentration of phenylcarbinol in aromatic groups, and then it is expected to explore them as luminescent sensor of phenylcarbinol. Mixed Ln-MOFs16,17,28and29exhibit typical luminescent response in the mixtures of glycol and1,4-dioxane. Ln-MOF28as a new luminescent "traffic lights" monitor gives fast response and variable luminescent colors visible to the naked eyes, which is a promising monitor the condensation reaction process of glycol into1,4-dioxane.4. Novel isostructural Ln-MOFs30-33were built through ID lanthanide chains using ligand H2FDA and contain similar triangular and rhombic channels along [1,1,0] direction and similar elliptic and butterfly-shaped channels along [1,0,1] direction. This framework can be simplified an unreported3,3,3,3,4,4,20-connected topology the short (Schla fli) vertex symbol{3·42}2{312·442·528·644·734·830}2{32·4}8{34·42}3. Luminescent measurements indicate that Ln-MOFs30-33can be explored as a luminescent sensor of phenylcarbinol in different kinds of alcohol solvents. |
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