Synthesis, Separation And Supramolecular Self-assembly Of Cyclopentyl Guar Ring

Superamolecular Chemistry is a kind of chemistry which is different from common chemistry that bases on non-covalent bond interactions as vander waals force, H-bond, ?-?stacking form some subjects that have some particular functions.Cucurbit[n]urils is a new kind of highly symmetric macrocycles which is developed after the crown ethers,cyclodextrins,calixarenes in the field of supramolecular chemistry.However,because of the harsh solubility of common Cucurbit[n]urils,the further research on the properties and its application of Cucurbit[n]urils have been limited.This paper synthesized a kind of Cucurbit[n]urils which is different from common Cucurbit[n]urils,whose waist is substuted by cyclopentyl,whose solubility in water and organic solvent as DMSO is better than the common Cucurbit[n]urils.The paper constructed the supramolecular self assembly of Cy P6Q6 with alkali metal,alkalineearth metals,rare earth metals respectively,and characteriz--ed them by X-ray single crystal diffraction,X-ray powder diffraction and IR spectrum.We also used cyclopentyl substituted glycoluril with ordinary glycoluril dimer in concentrated hydrochloric acid to synthesize a new type of cyclopentyl substituted Cucurbiturils,and characterized the crystal structure of the self assembly of this cucurbiturils with Er.The results show that the Cy P6Q6 form 1:1 supramolecular complexes with La³⁺?Ce³⁺?Pr³⁺?Nd³⁺,and the complex of Cy P6Q6 with La³⁺?Ce³⁺is similar to the complex of Cy P6Q6 with Pr³⁺?Nd³⁺.Due to the nature of the rare earth metal itself,the complexes with La³⁺?Ce³⁺?Pr³⁺?Nd³⁺presents a certain regularity.The effect of Cy P6Q6 on the separation of light rare earth metals was studied by means of energy spectrum characterization,our findings indica--te that enrichment effect of Cy P6Q6 on Nd is worse than other three light rare earth metals,there is little Nd in the in the mixture of La³⁺?Ce³⁺?Pr³⁺?Nd³⁺.Therefore, we can use Cy P6Q6 to separate the Nd from the light rare earth mixture.Cy P6Q6 form 1:2 supramolecular complexes with k+which is similar to report in the pre--vious literatures,and we can see the obvious nano-pore between the molecules;Cy P6Q6 for--ms 1:1 supramolecular complexes with Ca²⁺?Sr²⁺which is different from the complexes with k+,there is no nano-pore between the molecules.In this paper, a kind of molecular clip and a small molecular self assembly weresynthesized,X-ray single crystal diffraction indicates that molecular clip crystal belongs to the monoclinic,P21/npoint group,a=11.023?7??,b=17.413?11??,c=12.612?8??,?=90°,?=99.601?17?°,?=90°,V=2386.88?³,Z=48,R=0.08;small molecular self assembly belongs to triclinic,P-1 point group, a=8.3318?5??,b=15.4294?9??,c=15.8378?9??,?=66.147?2?°,?=77.057?2?°,?=77.504?2?°,V=1796.64?³,Z=2,R=0.09. Quantum chemistry calculation shows that the molecular clip structure has no imaginary frequency,Dipole moments equals 1.530×10-29 cm,therefore, the compound has good solubility and stability in polar organic solvents;In--teractions between the self assembly is H-bond and electrostatic interaction.