本論文主要探討過渡金屬鹵化物之巨分子化學研究。此類化合物 結構已用單晶X-ray鑑定出,結構特性則利用FT-IR與'H-NMR光譜 鑑定,並以熱重量分析(TGA)和微差熱掃瞄量計(DSC)儀器測試瞭解其熱性質。 4,4'-三亞甲基二吡啶配位基與過渡金屬鋅、鎘、汞、銅、錫和鉑二價金屬鹵化合物及HCl(aq)或HBr(aq)反應可以得到下列化合物:(H2mpd) ZnCl4×H2O,1;(H2mpd)CdBr4,2; (H2mpd)HgCl4×H2O,3;(H2mpd) CuCl4,4;(H2mpd)CuBr4×H2O,5;(H2mpd)SnCl6×H2O,6;(H2mpd) PtCl4×H2O,7。化合物1~7中質子化的4,4'-三亞甲基二吡啶經由M-X---H-Y (M = 金屬;X = Cl,Br;Y = N,C)與金屬陰離子連結。 由於氫鍵的影響,陽離子在每個化合物中具有不同的幾何形狀, 共可分成 anti-anti 與 gauche-gauche 兩種構形
This thesis discusses the supramolecular chemistry of divalent metal complexes containing protonated 4,4'-trimethylenedipyridine. Their structures have been determined by X-ray crystallography and characterized by FT-IR, 1H NMR, TGA and DSC. The reactions of the divalent metal halides with 4,4'-trimethylenedipyridine (mpd) and HCl or HBr afforded the following complexes: (H2mpd)ZnCl4×H2O, 1; (H2mpd)CdBr4, 2; (H2mpd)HgCl4×H2O, 3; (H2mpd)CuCl4, 4; (H2mpd)CuBr4 × H2O, 5; (H2mpd)SnCl6, 6 and (H2mpd)PtCl4 × H2O, 7. In these complexes, extensive M-X---H-Y (M = metal; X = Cl or Br; Y = N or C) hydrogen bondings are used to link the metal units to the protonated 4,4'-trimethylenedipyridine. Two types of conformation, anti-anti and gauche-gauche, are observed in the solid state for the cations.