Study On The Hybrid Self-Assembly Of Macrocyclic CB6-Metal Complexes

With the continuous development of supramolecular chemistry,it has attracted wide attention of scientists as an interdisciplinary subject.As one of the fourth generation of supramolecular host compounds,CB6 also aroused great interest.CB6(Cucurbituril)is a annular organic macrocyclic molecules,having a rigid wall,cavity in the middle,and high polarity port at both ends.Due to its special structure,therefore,it is used as a unique synthetic receptors in the aspect of Lord-guest chemistry and assembly of supramolecular structure,etc.It has become one of the concern hotpots in the field of supramolecular chemistry in recent years.In this paper,based on the related work of the laboratory related to the design and syntheses of supramolecules involving the organic macrocyclic pumpkin-shaped(CB6),four novel supramolecular crystals of 1-4 have successfully been synthesized by means of introducing copper(?),Zinc(?),cobalt(?),or nickel(?)complex of 8-hydroxyquinoline5-sulfonate:1.[Cu(Hqs)2][Na2(CB6)(H20)8]·6H2O,2.[Zn(Hqs)2][Na2(CB6)(H20)8]·6H2O,3.[Co(Hqs)2][Na2(CB6)(H20)8]·6H2O,4.[Ni(Hqs)2][Na2(CB6)(H20)8]·6H2O(where Hqs=8-hydroxyquinoline-5-sulfonate),crystal structures have been determined by X-ray diffraction method in order to analyzes the crystal structure and supramolecular weak interactions.The X-ray analyses showed that complex 1 was crystallized in Triclinic,Pi space group,a=11.843(2)A,b=12.381(3)A,c=15.328(3)A,a=110.884(4)°,?=112.428(4)°,?=91.520(3)°,V=1906.3(7)A3,Z=1,F(000)=935,Dcalc=1.572g/cm3,?=0.459 mm-1,R1[I>2?(I)]=0.0489 and wR2(all data)=0.1612;complex 2 was single crystal complexes in monoclinic system,a-16.328(3)A,b=13.643(3)A,c=20.836(8)A,?=119.35(2),V=4045.7(19)A3,Z=1,Dcalcd(g/cm3)=1.542,?(mm-1)=0.473,R1[I>2?(I)]=0.0544 ? wR2(all data)=0.1237;Complex 3 was crystallized in Triclinic,Pi space group,a=11.849(3)A,b=12.490(2)A,c=15.090(3)A,a=110.04(2)°,?=112.47(3)°,?=91.91(2)°,V=1903.70(3461)A3,Z=1,F(000)=913,Dcalc=1.539g/cm3,?=0.395mm'1,R1[I>2?(I)]=0.0598,and wR2(all data)=0.1475;Complex 3,Triclinic,Pi space group,a=11.862(2)A,b=12.470(3)A,c=15.165(3)A,?=110.26(3)°,p=112.52(3)°,?=91.71(3)°,V=1909.5(10)A3,Z=1,F(000)=934,Dcalc=1.566 g/cm3,?=0.427 mm-1,R1[I>2?(I)]=0.0518 and wR2(all data)=0.1169.The crystal structure showed that:complexes 1,3,4 exhibit similar 1D-coordination polymer structures,indicating that the synthetic strategy may also be suitable for other similar transition metal complexes.And the structure of the complexes 1 and 2 different demonstrated different impact of metal complexes center complexes of ligand structure.Our results may be significant for the supramolecular application of the macrocyclic CB6 and its family.