Modified Resorcin[4]arenes With Phosphoric And Sulfonic Groups And Their Self-assembly Behavious With Metal Ions

In this thesis, a series of derivatives containing coordination site weresynthesized by introducing functional groups onto the calix[4]resorcinarenesframework, either at the C-2positions of the aromatic rings to form cavitands whichcould complex with alkali metals, alkali earth metals and transitiom metals. We havesynthesized two types of calix[4]resorcinarenes with different substituent group (R1=H or R1=CH3) at C-2site in high yelid(1a-1e,2a-2e).Reaction of two aforementioned calix[4]resorcinarenes with PCl3and oxidizedafforded chlorinated phosphonate(3a-3e,4a-4e)and chlorinated thiophosphonate(9a-9e,10a-10e)derivatives presenting P(V) moieties as bridging unites. And furtherhydrolyzed to phosphonate(5a-5e,6a-6e)and thiophosphonate (11a-11e,12a-12e).In a addition, we synthesized a series of derivatives of calix[4]resorcinareneswith sulfonic, amido and sulfydryl groups in the presence of formalin:2-methylene-sulfo-resorcin[4]arene(13a-13e),2-methylene-amido-resorcin[4]arene(14a-14e),2-methylene-sulfydryl-resorcin[4]arene(15a-15e).All of the derivatives were characterized with the FT-IR spectroscopy,1H NMR,31P NMR and element analyses, and C-propyl tetrakis(O,O-phosphorus)-bridgedcalix[4]resorcinaol(5b), C-iso-butyl-tetrakis(O,O-phosphorus)-bridgedcalix[4]resorcinaol(5d), C-propyl-2-methyl-tetrakis(O,O-phosphorus)-bridgedcalix[4]resorcinaol(6b), C-iso-butyl-2-methyl-tetrakis(O,O-phosphorus)-bridgedcalix[4]resorcinaol(6d), C-iso-butyl-2-methylene-sulfo-resorcin[4]arene(12d),C-methyl-2-methylene-amido-resorcin[4]arene(14a), C-propyl-2-methylene-amido-resorcin[4]arene(14b) and C-iso-butyl-2-methylene-amido-resorcin[4]arene(14d)were characterized by single-crystal X-ray diffraction.On the basis of the synthesizd organic compounds, we studied the coordinationof these derivatives with metal salts. As for the phosphonate derivatives,multi-component compounds were synthesized which contained the calixarene andthe units of CuPynor CuCl2Pyn:[5b·CuCl(NC5H5)4]16,[5d·CuCl(NC5H5)4·Cu(NC5H5)3(H2O)3]17,[5d·CuBr(NC5H5)4·Cu(NC5H5)3(H2O)3]18,[6d·CuCl(NC5H5)4·CuCl2(NC5H5)4]19. And we discussed the double clay layerstructure of sulfo derivatives with sodium ions:[13d·Na4(H2O)6·CH3CN]20.