無機化合物自我組合之研究

本論文主要利用多芽配位基與過渡金屬反應，探討無機分子間的自我組合，包含了兩個部分。第一部分兩種新型並具有對掌性的配位高分子化合物Cu(nic)2(H2O)•CH3OH (nic = nicotinate)，1及 Co(nic)2•H2O，2已被合成並以單晶X-ray繞射儀鑑定及紀錄之；結構1和2具有對掌性的空間群P3221與C2。以二當量菸鹼酸(nicotinic acid)配位基分別與一當量二價過渡金屬CuCl2•2H2O和Co(NO3)2•6H2O反應可得化合物1及2。菸鹼酸配位基以吡啶環上的氮原子及羧酸基上的單芽氧鍵結或雙芽氧螯合的方式橋接化合物1與2的中心金屬，並形成二維或三維的網狀結構；化合物1的中心銅原子形成五配位的扭曲四角錐，化合物2的中心鈷原子則形成六配位的扭曲八面體。化合物1形成開放式的孔洞結構，並含可移動的客體甲醇分子，化合物2則形成層狀平面格子的結構。第二部分以N, N S-di(2-methoxyphenyl)formamidine (o-HDMophF)配位基與過渡金屬鹵化物反應，可得到一系列含o-HDMophF配位基的過渡金屬化合物CuCl2•(o-HDMophF)，3；[CoCl4][o-H2DMophF]2，4；[CoBr4][o-H2DMophF]2，5；CdCl2(o-HDMophF)2，6；NiCl2(o-HDMophF)2，7；MnCl2(o-HDMophF)2，8；PdCl2(o-HDMophF)2，9以及 Cu2(o-DMophF)2，10，以上八種化合物的單晶結構均以單晶X-ray繞射儀鑑定並紀錄之。在結構3 ~ 5中，主要利用中性o-HDMophF配位基或質子化的o-H2DMophF+配位基經由C-H•••X及N-H•••X ( X= Cl, Br)等多種不同形式的氫鍵及芳香環間π - π作用力與金屬反應形成超分子結構。化合物6 ~ 8，均以成對的中性的配位基以氨基上的氮原子與甲氧基上的氧原子以螯合的方式和兩個cis的氯原子鍵結到中心金屬，形成具對掌性的(chiral)六配位扭曲八面體。化合物9亦以成對的中性配位基以氨基上的氮原子以單芽配位的方式和兩個trans的氯原子與中心金屬鍵結，形成四配位扭曲平面四邊形。化合物6 ~ 9的結構中，配位基o-HDMophF 以新型的雙芽單螯合及單芽鍵結與中心金屬鍵結。在化合物10中，兩個銅原子被兩個陰離子的o-DMophF−配位基橋接而形成雙核化合物，銅原子間的距離為2.5748(10) Å。銅原子在化合物10中的鍵結模式趨近於直線型。

關鍵字

構形；無機；氫鍵；菸鹼酸；自我組合

並列摘要

This thesis includes two parts discussing the self-assembly of inorganic molecules containing polydentate ligands. Part I. The syntheses and crystal structures of two new chiral coordination polymers of the types Cu(nic)2(H2O)•CH3OH (nic = nicotinate), 1, and Co(nic)2•H2O, 2, are reported. The reactions of nicotinic acid with CuCl2•2H2O and Co(NO3)2•6H2O afforded complexes 1 and 2, respectively. Single-crystal X-ray crystallography structure determinations show that complexes 1 and 2 crystallize in the space groups P3221 and C2, respectively. The Cu(II) centers in 1 adopt a slightly distorted square pyramid geometry, while the Co(II) centers in 2 exhibit a distorted octahedral coordination geometry. The metal centers in 1 and 2 coordinate to both the pyridyl and carboxylate groups to form 3-D and 2-D framework structures, respectively. Complex 1 exhibits open channels that are occupied by removable CH3OH molecules, while complex 2 shows a planar molecular grids. Part II. The reactions of N, N S-di(2-methoxyphenyl)formamidine (o-HDMophF) with transition metal halide complexes afforded CuCl2 • (o-HDMophF), 3, [CoX4][o-H2DMophF]2 (X = Cl, 4; Br, 5), MCl2(o-HDMophF)2 (M = Cd, 6; Ni, 7; Mn, 8; Pd, 9) and Cu2(o-DMophF)2, 10. These complexes were characterized by single-crystal X-ray diffraction method and elemental analyses. The neutral o-HDMophF ligands in complexes 6 - 8 and 9 are coordinated to the metal centers in new bidentate and monodentate fashions, respectively. In the crystal structures of 3 - 9, C-H•••X and/or N-H•••X (X = Cl, Br) interactions are found to link the metal units to the o-HDMophF ligand or its protonated cation (o-H2DMophF+). The neutral o-HDMophF compound in 9 adopts the s-trans-anti-s-trans-conformation, while those in complexes 6 – 8 and 9 adopt the s-trans-anti-s-trans- and s-cis-anti-s-trans- conformations, respectively. The o-H2DMophF+ cations of complexes 4 and 5 adopt the s-cis-syn-anti-s-trans and s-trans-anti-anti-s-trans conformations. In complex 10, the two Cu atoms are bridged by two o-DMophF- ligands to give a binuclear structure, in which the Cu∙∙∙Cu separation is 2.5748(10) Å. The geometries of the copper atoms are linear.

並列關鍵字

Inorganic ； Nicotinic acid ； comformation ； Hydrogen bonds ； Self-assembly

參考文獻

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無機化合物自我組合之研究

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