直線型多核金屬串錯合物及三核鎳錯合物與金屬紫質超分子組裝之合成及研究

Abstract

本論文之研究目標為直線型多核金屬串錯合物之合成及三核鎳錯合物與金屬紫質之超分子組裝。 新型2,7-bis(α-pyrimidylamino)-1,8-naphthyridine【H2bpmany】和2,7-bis(dipyridyldiamino)-1,8-naphthyridine【H4bdpdany】配基可利用鈀金屬的催化由2,7-dichloro-1,8-naphthyridine和2-aminopyrimidine或dipyridyldiamine反應而得。 H2bpmany配基可與金屬離子鍵結，形成五核金屬串錯合物[Ni4Ru(μ5-bpmany)4(NCS)2] 1、六核金屬串錯合物[Ni6(μ6-bpmany)4X2]Cl (X = Cl– 2；, X = NCS– 4)和[Co6(μ6-bpmany)4X2](BF4) (Y = Cl– 6；Y = NCS– 8)。而一個電子氧化之六核金屬串錯合物[Ni6(μ6-bpmany)4X2](BF4)2 (X = Cl– 3；X = NCS– 5) 和[Co6(μ6-bpmany)4X2](BF4)2 (Y = Cl– 7；Y = NCS– 9)可由六核鎳或六核鈷金屬串錯合物與相關的氧化劑FcBF4或NOBF4反應得到。 由X-ray單晶繞射解析可知，一個電子氧化錯合物3和5之最內部Ni-Ni鍵距較錯合物2和4分別增長約0.08和0.06 Å。 H4bdpdany配基可以全反向式及全順向式之配位模式與金屬離子鍵結。 以全反向式，H4bdpdany配基可鍵結兩個CuⅡ，形成一雙核銅金屬錯合物[Cu2(H4bdpdany)(OH)(H2O)](PF6)3 10，每個CuⅡ皆為四方角錐之配位環境，且Cu…Cu距離為2.959(2) Å。以全順向式，去質子化bdpdany4–配基可作為十牙基與十個鎳金屬離子鍵結成直線型，且錯合物[Ni10(μ10-bdpdany)4X2]2+也已初步由MALDI-TOF及ESI質譜鑑定證實。 利用吡啶衍生物修飾三核鎳金屬串錯合物兩端，可得到四個組裝單元[Ni3(dpa)4X2] (X = 4-PyCOO– 13a；X = 3-PyCOO– 13b；X = 4-PyCC– 14a；X = 3-PyCC– 14b)，並將其與金屬紫質反應，可行成穩定的聚合物及寡聚物。新穎輪軸狀寡聚物[Ni3(dpa)4X2][ZnTPP]2 (X = 4-PyCOO– 15a；X = 3-PyCOO– 15b；X = 4-PyCC– 16a；X = 3-PyCC– 16b)及一維聚合物{[Ni3(dpa)4X2][MnTPP]}n(ClO4)n (X = 4-PyCOO– 18a；X = 3-PyCOO– 18b；X = 4-PyCC– 19a；X = 3-PyCC– 19b)、{[Ni3(dpa)4(4-PyCC)2][CoTPP]}n 20a已經被合成，並獲得其X-ray單晶繞射結構。由電子吸收光譜可知，錯合物內之三核鎳金屬串錯合物與金屬紫質間並無明顯的交互作用。

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.