Syntheses and Studies of Linear Multinuclear Metal String Complexes and Supramolecular Assembly of Trinickel Complexes Incorporating Metalloporphyrins

• Main Authors: Ting-Bin Tsao, 曹廷賓
• Other Authors: Shie-Ming Peng
• Format: Others
• Language: zh-TW
• Published: 2005
• Online Access: http://ndltd.ncl.edu.tw/handle/39946573262955628852

博士 === 國立臺灣大學 === 化學研究所 === 94 === The aim of this thesis is to investigate the synthesis of novel linear multinuclear metal string complexes, and supramolecular assembly of trinickel complexes incorporating metalloporphyrins. The new 2,7-bis(α-pyrimidylamino)-1,8-naphthyridine (H2bpmany) and 2,7-bis(dipyridyldiamino)-1,8-naphthyridine (H4bdpdany) ligands have been synthesized by palladium-catalyzed cross-coupling of 2,7-dichloro-1,8-naphthyridine with 2-aminopyrimidine or dipyridyldiamine, respectively. The H2bpmany ligand can bind metal ions, forming pentametal string complex [Ni4Ru(μ5-bpmany)4(NCS)2] 1, and hexametal string complexes [Ni6(μ6-bpmany)4X2]Cl (X = Cl– 2；X = NCS– 4) and [Co6(μ6-bpmany)4X2](BF4) (X = Cl– 6；X = NCS– 8). The one-electron oxidized hexametal string complexes [Ni6(μ6-bpmany)4X2](BF4)2 (X = Cl– 3；X = NCS– 5) and [Co6(μ6-bpmany)4X2](BF4)2 (X = Cl– 7；X = NCS– 9) were generated by reacting the hexanickel or hexacobalt complexes with the corresponding oxidant FcBF4 or NOBF4, respectively. X-ray structural studies reveal the internal Ni-Ni bond distances in one-electron oxidized complexes 3 and 5 are ca. 0.08 and 0.06 Å longer than that in 2 and 4, respectively. The H4bdpdany ligand can bind metal in two conformations, all-anti and all-syn forms.In all-anti form, H4bdpdany ligand can bind two CuⅡ ions, forming dicopper complex [Cu2(H4bdpdany)(OH)(H2O)](PF6)3 10. Each CuⅡ ion is close to square pyramidal conformation, and the Cu…Cu distance is 2.959(2) Å. In all-syn form, deprotonated bdpdany4– ligand can act as a decadentate bind with ten nickel ions in a linear arrangement, and the complexes [Ni10(μ10-bdpdany)4X2]2+ have also primitively been characterized by MALDI-TOF and ESI mass spectrum. The pyridine derivatives were attached to the ends of linear trinickel complexes to produce four building blocks [Ni3(dpa)4X2] (X = 4-PyCOO– 13a；X = 3-PyCOO– 13b； X = 4-PyCC– 14a；X = 3-PyCC– 14b), which were then react with metalloporphyrins to form stable polymers and oligomers. The novel “wheel-and-axle” shaped oligomers, [Ni3(dpa)4X2][ZnTPP]2 (X = 4-PyCOO– 15a；X = 3-PyCOO– 15b；X = 4-PyCC– 16a；X = 3-PyCC– 16b), and one-dimensional polymers, {[Ni3(dpa)4X2][MnTPP]}n(ClO4)n (X = 4-PyCOO– 18a；X = 3-PyCOO– 18b；X = 4-PyCC– 19a；X = 3-PyCC– 19b) and {[Ni3(dpa)4(4-PyCC)2][CoTPP]}n 20a, [dpa– = di(α-pyridyl)amido anion; TPP = meso-tetraphenylporphyrinato dianion], have been synthesized and their structures were determined by X-ray diffraction. The UV/Vis spectra indicate the absence of any noticeable interaction between the linear trinickel complexes and metalloporphyrins in these chains.