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Scientists Reveal Stereocontrolled Self-Assembly and Self-Sorting of Supramolecular Lanthanide Nano-Cages

 

 

Lanthanide-containing molecules have a wealth of stimulating applications, e.g. luminescent probes, contrast agents, magnetic or superconducting materials. A massive number of self-assembled three-dimensional (3D) molecular edifices have been built based on elaborate geometrical consideration when combining metal ions (M) and organic ligands (L). 

On contrast to the most often exploited transition metals, non-transition metals, especially the rare-earth elements, are far less utilized in the directed self-assembly process. However, the difficulties in predicting the coordination numbers and coordination geometries for lanthanide make a controlled self-assembly toward a predetermined structure rather challenging.

A team led by Prof. SUN Qingfu from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, has recently reported the first examples of stereoselective self-assembly of chiral luminescent europium coordination tetrahedral cages and their intriguing self-sorting behavior.

Two pairs of R and S ligands are designed on the basis of the pyridine-2,6-dicarboxamide coordination unit, bis(tridentate) L1 and tris(tridentate) L2. Corresponding chiral Eu4(L1)6 and Eu4(L2)4 topological tetrahedral cages are independently assembled via edge- and face-capping design strategies, respectively.

The chirality of the ligand is transferred during the self-assembly process to give either Δ or Λ metal stereochemistry. The self-assembled cages are characterized by NMR, high-resolution ESI-TOF-MS, and in one case by X-ray crystallography. Narcissistic self-sorting is observed in the self-assembly process when two differently shaped ligands L1 and L2 are mixed.

More impressively, distinct self-sorting behavior between Eu4(L1)6 and Eu4(L2)4 coordination cages is observed for the first time when racemic mixtures of ligands are used, revealing the inherent differences in mechanical coupling effect of the two topological tetrahedral complexes.

Researchers envisaged that chiral luminescent lanthanide tetrahedral cages could be used in chiroptical probes\sensors and enantio-selective catalysis. Related works on these sides are currently underway.

This research has been published recently in J. Am. Chem. Soc., one of the top journals in the chemistry field. (DOI: 10.1021/jacs.5b03972)

This research was financially supported by the National Natural Science Foundation of China, etc.

 

 

 

 

Stereocontrolled Self-Assembly and Self-Sorting of Supramolecular Lanthanide Nano-Cages(Image by Prof. SUN's group)

 

Contact:

 

Prof. SUN Qingfu

Fujian Institute of Research on the Structure of Matter

Chinese Academy of Sciences

Email:qfsun@fjirsm.ac.cn

 

 


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