Chemistry of Polynuclear Copper(I) Complexes and Coordination Polymers Supported by Formamidine &; Formamidinate Ligands

• Main Authors: Hsuan-Chou Lin, 林玹州
• Other Authors: Jhy-Der Chen
• Format: Others
• Language: en_US
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/s83vn7

碩士 === 中原大學 === 化學研究所 === 103 === This thesis discusses the structures and properties of polynuclear copper(I) complexes and coordination polymers supported by formamidine and formamidinate ligands. One-pot solvothermal reactions of 3-aminopyridine, 4-chloroaniline, 4-bromoaniline, 4-iodoaniline, or 4-amino-2-chloropyridine with triethylorthoformate and CuX (X = Cl–, Br– , I–) afforded complexes [Cu3(3-pyf)2Cl3]n, 1, [Cu4(3-pyf)4Br4], 2, [Cu(3-pyf)I]n, 3, [Cu2(4-cphf)2], 7, [Cu(4-Hbphf)4Br2], 8 , [Cu2(4-iphf)2], 10 and [Cu2(2-cpf)2], 11, whereas the reactions of CuX (X = Cl–, Br–) with 3-aminopyridine and 4-bromoaniline, in a Methanol (MeOH) or tetrahydrofuran (THF) or acetonitrile (ACN) solution containing triethylorthoformate and sodium hydroxide gave complexes [Cu4(3-pyf)4], 4, {[Cu8(3-pyf)8]·5THF}, 5, [Cu(3-pyf)]n, 6, and[Cu2(4-bphf)2], 9, which were characterized by X-ray crystallography. Complex 1 is a 3D coordination polymer with (62.82.102)(62.8)2 - sur; bbf-3,4-Ccm topology, complex 2 is a very rare example of tetranuclear paddlewheel complex containing rhombohedral Cu2X2, complex 3 is a 1D chain structure, complex 4 is a tetranuclear complex with cuprophilicity, complex 5 is the first octanuclear complex with Cu(I)---Cu(I) interactions, complex 6 is a 2D structure of {44.62} topology, complexes 7, 9–11 are dinuclear copper(I) complexes that shows different distances of Cu(I)---Cu(I), and complex 8 is a dinuclear complex containing rhombohedral Cu2Br2 unit.