Synthesis,Structure,and Cation-Exchange of Metal-Salicyaldimine Complexes

[[abstract]]本實驗成功合成出兩種含有亞胺酚基形式之有機配子H2L1及H2L2，並以這兩種有機配子與金屬進行自組裝反應及陽離子置換實驗。 本實驗裡用H2L1與Zn(OAc)2以水熱法進行自組裝反應得到一維鋸齒狀配位聚合物[Zn(L1)(H2O)] (1)，並使用化合物1與多種金屬離子以陽離子置換方式進行反應，在產物1/Ni(NO3)2-11 (1a)、1/Ni(NO3)2-12 (1b)、1/Cu(NO3)2-11 (1c)、1/Cu(NO3)2-12 (1d)、 1/Fe(NO3)3-11 (1i)、1/Fe(NO3)2-12 (1j)、1/Pd(NO3)2-11 (1k)及1/Pd(NO3)2-12 (1L)的系統下經由粉末X光繞射及單晶X光繞射鑑定得知，在置換金屬離子的同時，使結構上也產生了些許的改變。然而在產物1/Co(NO3)2-11 (1e)、1/Co(NO3)2-12 (1f)、1/Mn(NO3)2-11 (1g) 及1/Mn(NO3)2-12 (1h)的系統下沒有產生離子置換產物。 此外，本實驗分別使用H2L1及 H2L2與氯化銅與硝酸銅以水熱法或室溫擴散實驗進行自組裝反應，得到了配位化合物[Cu(HL1)Cl]．2H2O (2)跟[Cu(HL2)Cl] (3)，以及聚合物[Cu(HL2)(NO3)] (4)。化合物4為一維鋸齒狀結構，由螯合－橋接的硝酸根與[Cu(HL2)]+錯合離子連接而成。[[abstract]]Two Schiff bases, H2L1 and H2L2, have been designed and synthesized from the condensation reaction of 2-(aminomethyl)pyridine and corresponding salicylaldehydes. Reactions of H2L1 and H2L2 with zinc and copper salts afforded corresponding metal–salicyaldimine complexes [Zn(L1)(H2O)] (1), [Cu(HL1)Cl]．2H2O (2), [Cu(HL2)Cl] (3), and [Cu(HL2)(NO3)] (4). All of these compounds were characterised using infrared spectroscopy, single crystal X-ray diffraction, and powder X-ray diffraction. Complexes 2 and 3 have discrete mononuclear structures, while 1 and 4 exhibit novel 1D chain structures. When the microcystalline samples of 1 were immersed in the aqueous solutions of M(NO3)2 (M = Ni, Cu, Co, Mn, Pd) and Fe(NO3)3, cation-exchange was achieved in the cases of Ni2+, Cu2+, Pd2+, and Fe3+, of which a mononuclear complex [Ni(L1)(H2O)3] (1Ni) and a 1D chain polymer [Cu(L1)]．3H2O (1Cu) were structure characterised by single crystal X-ray diffraction. These results significantly indicate that cation–exchange may offer as a way to synthesize new coordination structures that cannot be obtained from direct self–assembly synthesis route.[[note]]碩