Chao-Ying Gao

Particular Handedness Excess through Symmetry-Breaking Crystallization of a 3D Cobalt Phosphonate.

A 3D chiral cobalt phosphonate has been obtained from achiral precursors in the absence of chiral inducers. Remarkably, the bulk sample is largely enantio-enriched with particular handedness through symmetry-breaking crystallization in spite of multiple repeated experiments. Moreover, protonation of this chiral material introduces Brønsted acid sites, the structure of which is unique to the heterogeneous phase for the ring opening of epoxies.

A microporous Cd-MOF based on a hexavalent silicon-centred connector and luminescence sensing of small molecules

Solvothermal reaction of Cd2+ cations with a silicon-centered carboxylic acid (H6L) afforded a novel metal–organic framework, namely, [Cd3L(H2O)5]·DMA·H2O (1). It is built from three {CdO6} clusters and organosilicone linkers to form a 3D porous framework. The steric organosilicone ligand is among the never documented examples. Interestingly, 1 exhibited spontaneous formations of microtubular crystals, the phenomenon of which is rarely reported among the metal–organic coordination assemblies. In addition, the luminescence properties of 1 dispersed in different organic solvents have been investigated, displaying turn-on and turn-off luminescence responses for n-butanol and acetone, respectively.

Porous Anionic Uranyl–Organic Networks for Highly Efficient Cs+ Adsorption and Investigation of the Mechanism

Exploitation of new materials for the removal of long-lived and highly radioactive actinides and their fission products produced in the nuclear fuel cycle is crucial for radionuclide management. Here, two rare porous anionic uranyl-organic frameworks (UOFs) have been successfully synthesized by a judicious combination of the tetratopic carboxylate ligand 1,3,6,8-tetrakis( p-benzoic acid)pyrene (H4TBAPy) and D3 h-symmetrical triangular [UO2(COO)3]-. The resulting two compounds exhibit different architectures, albeit with similar coordination modes. Of interest is that they have excellent adsorption performance on Cs+ from aqueous solution. The high removal efficency would make them promising in applications of radioactive waste management. Notably, the framework of compound 2, [(CH3)2NH2]4[(UO2)4(TBAPy)3]·22DMF·37H2O is sufficiently robust to allow the accessibility of intriguing single crystals of a Cs+-adsorbed derivative, which helps to elucidate the adsorption mechanism. The structural, bonding, and spectroscopic properties of the above compounds are examined using relativistic density functional theory (DFT). It is found that the adsorption toward cesium on UOFs is energetically favored, which features largely ionic bonds and is dominated by electrostatic attraction.