Syntheses And Structures Of Complexes By Using Sodium P-Sulfonatocalix[4] Arene As Building Blocks

Calixarenes, which are called the third generation host compounds of supramolecular, are macrocyclic molecules with unique cavities in the different size and the different shape like crown ethers and cyclodextrins. There are several reasons for the current widespread interest in calixarenes. An important one is the remarkably simple way (single-step procedure) used for the synthesis of the parent compounds. In addition, lower and upper rim functionalization of these macrocycles has resulted in a massive expansion in the range of derivatives available. Of the large family of water-soluble calixarenes that have been synthesised in recent times, chemist have been interested in the solid state supramolecular chemistry of p-sulfonatocalix[n]arenes (where n = 4, 5, 6, 8,). Whilst not only offering the opportunity to employ water as a benign solvent for reaction or crystallisation, these calixarenes present hydrophobic cavities for guest inclusion of organic molecules, although the inclusion of water is also possible. The'upper rim'sulfonate groups are capable of interacting with a range of organic, charged organic, inorganic or hydrogen-bond donor species. Furthermore, these watersoluble calixarenes also display interesting biological behaviour.It was studied that p-sulfonatocalix[4]arena was not easily coordinate with metal ions. However, in the most of the solid states sulphonate complexes, sulphonates often know as charge balance ions. At the same time, neutral ligands often paly important roles in the sulfonate polymers and often create novel structures. Organotin carboxylates have attracted considerable attention due to their wide applications in many fields. Therefore, it is very important to synthesize novel organotin compounds and study their properties. In this paper, we design to synthesize three supramelocular complexes. They are p-sulfonatocalix[4]arene with silver ion, p-sulfonatocalix[4]arena with silver ion and ethylenediamine, p-sulfonatocalix[4]arena with Bu2SnO. The experimental results as following: 1. The synthesis and characterization of the target host molecular. At first, we get p-t-butylcalix[4]arene by the reaction of p-t-butylphenol and HCHO. Then get calix[4]arene by treating p-t-bucalix[4]arene with AlCl3. At last, we get p-sulfonatocalix[4]arene by the reaction of calix[4]arene and H2SO4(98%). All the three compounds above were characterized by 1H NMR and IR spectrum. The result was the same as that in the references.2. complex(1) [Ag(H2O)Na(H2O)3SC4]·3H2O was synthesized by sodium p-sulfonatocalix[4]arene and Ag+. Its crystal was obtained by slowly evaporation of its aquation at room temperature. Single-crystal X-ray diffraction has indicated that in the solid states of complex(1), one oxygen atom of the sulphonates combine to Ag+, one Na + was combined by three water molecular. The Ag+ and Na + were bridged by one other water molecular.3. complex(2) [Ag₈(L₈)(SC₄)₂]·25H₂O was synthesized by sodium p-sulfonatocalix[4]arene and Ag+, using ethylenediamine to adjust pH=11. Its crystal was obtained by slowly evaporation of its aquation at room temperature. Single-crystal X-ray diffraction has indicated that complex(2) have novel structure compared to the other reported complexes contained sulfonatocalix[4]arene, metal ions and neutral ligands three species. In the solid state of complex(2), four Ag+ and four ethylenediamine formed a four member macrocycle. Two such macrocycles were combined together by Ag-Ag metal bond. Two sulphonates of two p-sulfonatocalix[4]arene extend to the two macrocycle which formed typical bi-layer structure.4. complex(3) [Sn (Bu)2 (H2O)3Sn2 (Bu2O)2SC4(H2O)3]·6H2O was obtained by the reaction of p-sulfonatocalix[4]arene and Bu2SnO in 70% alcohol under 60℃. Its crystal was obtained by slowly evaporation of its filtrate at room temperature. Single-crystal X-ray diffraction has indicated that in complex(3), there have two kinds of Bu2Sn. One is that one oxygen atom of the sulphonates directly combine to its Sn, and the other is that a four member Sn2O2 cycle has formed between two Bu2SnO. Then two sulphonates of two p-sulfonatocalix[4]arene combined to the Sn atom of Sn2O2 to form 1D chain. We have found that the ratio of p-sulfonatocalix[4]arene and Bu2SnO won't influence the structure of complex(3). All the three compounds above except complex(1) were characterized by IR spectrum.