Syntheses And Structures Of The Coordination Complexes Based On Calix[4]arene Derivatives

Calixarenes, which are called the third generation host compounds, are a class of well defined macrocyelic oligomers prepared by the reaction of tert-butylphenol and formaldehyde. Owing to their lower and upper rim functionalization of these macrocycles and good ability to form derivatives, they have acquired considerable attentions in recent years.In this paper, six novel coordination compounds were synthesized. They have been structurally determined by single-crystal X-ray diffraction analyses. In addition, compounds1-6have been further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and so on.1. Two three dimensional Cu(Ⅱ) compounds [Cu2(btb)3.5(C4AS)(H2O)]·2.5(H2O)(1) and [Cu2.5(btp)2(C4AS)()(H2O)3]·4.75(H2O)(2) have been hydrothermally synthesized (btb=1,4-bis(1,2,4-triazol-1-yl)butane, btp=1,5-bis(1,3,4-triazol-1-yl)pentane,=1,3,4-triazolate and C4AS=p-sulfonato-calix[4]arene). Topologically, structure1belongs to a3D (3,6)-connected net with the Schlafli symbol of (42·6)(46·68·8). In2, the C4AS links the Cu(II) atoms to form1D chains, which are further connected by the btp and to generate a3D (3,4,6)-connected framework with the Schlafli symbol of (62·8)(52·62·7·8)(54·62·7·87·9).2. Four new coordination polymers, namely,[Co4Na2(L)2(O)2(H2O)6]·7(H2O)(3),[Cu3Na2(L)2](4),[Zn6Na6(L)4(O)2(bbi)(H2O)4]·5(H2O)(5) and [Zn6Na6(L)4(O)2(btb)(H2O)4]·5(H2O)(6), where L=Tetra(carboxymethoxy)calix[4]arene, bbi=1,4-bis(1H-imidazol-1-yl)butane, have been synthesized and characterized by single-crystal X-ray diffraction. The structure of compound3is an intriguing2D self-penetrating network. Further, the π-π interactions among the L3anions link the2D networks into a3D supramolecular assembly. Compound4displays a corrugated2D (4,4) sheet with dangling arms. Each sheet is threaded by the dangling arms of two others, leading to an unusual3D polythreading framework.5and6show2D undulated sheet structures.