Studies On Design And Synthesis Of Novel Anion Receptors And Ethylene Oligomerization Behavior Of Later Transitional Metal Catalyst

A series of new neutral arylnickel(II) phosphine complexes bearing non-symmetric bidentate chelate ligands 3-aryliminomethyl-5-chloro-2-hydroxy- benzaldehyde have been synthesized, and the structure of representative complexes (2b and 2d) have been confirmed by X-ray crystallographic analysis. These neutral arylnickel(II) phosphine complexes have been investigated as catalysts for ethylene oligomerization. Using methylaluminoxane (MAO) as a cocatalyst, these complexes display high ethylene oligomerization activities. Catalytic activity of up to 4.6×106 g mol-1h-1 has been observed. The influence of Al/Ni molar ratio, reaction temperature, reaction period and pressure on catalytic activity was investigated. Moreover, a series of novel colorimetric anion sensors which bearing phenol O-H, hydrazone N-H groups, thiourea groups and thiosemicarbazones were designed and synthesized via simple processes. The receptor F3 could form supramolecular organic gel in DMF or DMSO solution. This organic gel possesses solution-Gel transition response upon the addition of anion. This organic gel could efficient detect F-, AcO- and H2PO4- conveniently. The receptors L1 and L2 could selectively"naked eyes"recognize Cl- in DMSO/H2O (9:1, v/v) solutions and AcO- in DMSO/H2O (7.5:2.5, v/v) solutions. A test paper based on L1 was developed which could detect F- and AcO- conveniently. Receptors M1 and M3 showed colorimetric single selectivity for I–. Moreover, M1 and M3 could selectively colorimetric detect Cl-, F- and AcO- in DMSO or DMSO/H2O solutions. Receptors 3a~3f employ 5-nitrophenylfural as signal group and thiosemicarbazone group as binding sites. Some of them could selectively colorimetric recognizes F-, AcO- and H2PO4- in DMSO solutions. The structures of these receptors were confirmed by single crystal X-ray diffraction. In the crystal, the molecular of the receptor self-assembled as link like or network supramolecular by hydrodgen bonds andπ-πstack action. The pincer type receptors A1~A5 which employ thiosemicarbazone group and phenol O-H group as binding sites, these receptors possess selective fluorescent recognition ability for F- and NO3-. In summar, in a series of anion receptors were synthesized, these receptor could selectively recognize F-, Cl-, I-, AcO-, H2PO4- and NO3-. The organic gel and anion test paper could efficiently and conveniently sense anions.