【作者】 娄本勇；

【导师】 陶偌偈； 周绪亚；

【作者基本信息】 河南大学 ， 无机化学， 2002， 硕士

【摘要】 作者以N，N’—二(2-氨乙基)草酰胺和两种醛类缩和制得了两种含有对称取代草酰胺桥基的Schiff碱配体N，N’-二(2-氨乙基)-草酰胺双缩邻氨基苯甲醛和N，N’-二(2-氨乙基)-草酰胺双缩(3-羧基水杨醛)，合成和表征了它们的Cu(Ⅱ)、Ni(Ⅱ)均双核配合物。循环伏安研究表明在N，N’-二(2-氨乙基)-草酰胺双缩邻氨基苯甲醛Schiff碱的桥联下两个金属离子表现出相同的电化学行为。而在N，N’-二(2-氨乙基)-草酰胺双缩(3-羧基水杨醛)配体的桥联下两个Ni(Ⅱ)表现出相同的电化学行为，两个Cu(Ⅱ)的电化学行为有着明显差异。 以邻氨基苯甲酸、草酸乙酯酰氯和1，3—丙二胺缩合制得了具有不对称草酰胺结构配体N-(2-羧基苯)·N -(3-氨丙基)草酰胺(oxca)，以它的Cu(Ⅱ)单核配合物为母体合成了系列Cu(Ⅱ)—M(Ⅱ)(M=Mn、Co、Ni、Cu、Zn)双核配合物[Cu(oxca)M(phen)2]ClO4·2H2O，用元素分析、红外光谱、电子光谱等对所合成配合物进行了表征。用循环伏安研究了以上五种配合物的电化学行为，表明在双核配合物中内部的铜离子容易被还原。通过变温磁化率的测量定量研究了Cu(Ⅱ)-Mn(Ⅱ)、Cu(Ⅱ)-Ni(Ⅱ)配合物分子内金属离子间的磁交换作用，得到它们的磁交换参数分别为J=-10.56cm-1和J=-17.08cm-1。研究表明Cu(Ⅱ)处在不对称的N3O的配位环境中与处在N4的配位环境中相比金属间的磁相互交换作用减小，并且Cu(Ⅱ)-Ni(Ⅱ)体系的变化尤为显著，这可能是由于O原子的电负性比N原子的电负性大，使Cu(Ⅱ)的d电子向其离域的程度增加，金属间的磁相互交换作用从而减小。 以单核片断Na[Cu(oxca)]·1.5H2O为母体采用“配合物为配体”的策略设计合成和表征了五种三核配合物[Cu(oxca)]2M·2H2O(M=Mn2+、Co2+、Ni2+、Cu2+、Zn2+)，循环伏安研究表明除[Cu(oxca)]2Zn·2H2O外在三核中两个Cu(Ⅱ)的电化学行为有着明显差异。在4-300K范围内测定了配合物[Cu(oxca)]2Co·2H2O变温磁化率，进行最佳拟和得到磁参数为J=-28.09cm-1，g=2.13,拟合因子F=3.81×10-3。 河南大学九九级硕士学位毕业论文 娄本勇 以单核片断 NaKu…］·1．SH。O为母体合成和表征了两种稀土－过渡金属异四核配合物厂叭OXCalhM（HZOh·SHZO（M补d，Gd＼研究了其电化学性质，并对［C3（OXCal］3Gm刃）。·SH刃体系进行了磁性研究，经最佳拟和得到的磁参数为J－0、537Cm‘，g＝l．955，拟合因于 F－5石SX 10J。J为较小的正值说明异四核单元中 一Cllh和Gd卜之间仅存在着微弱的铁磁相互作用。这是由于4f电子被外层电子屏蔽，其运动状态受配体的影响很小，即4f电子不易向配体离域，故造成了＊”的3d电子和 Gdy的4f电于间非常弱的磁交换作用。更多还原

【Abstract】 Through condensing N,N’-bis(2-aminoethyl)oxamide and two aldehydes we have synthesized and characterized two new Schiff base ligands with oxamido group ,namely N,N’- bis(2-aminoethyl) oxamido -bis(o- aminobenzaldehyde) (1) and N,N’-bis (2-amin-oethy l)oxamido -bis(3-carboxylsalicylidene) (2). New Cu(II),Ni(II) homobinuclear complexes have been synthesized and characterized. The studies by cyclic voltammetry show that two metal cations have the same electrochemical behavior bridged by the ligand (1) but two Ni(II) centers have the same behavior and two Cu(II) centers have different behavior bridged by the ligand (2).Through condensing o-aminobenzoic acid ,ethyl oxalyl chloride and 1,3 -propylenediamine, a new ligand N-(2-carboxyphenyl)-N’-(3-aminopropyl) oxamide(oxca) has been synthesized. Using mononuclear complex Na[Cu ( oxca)] -1.5H2O as building block we have synthesized five novel binuclear complexes [Cu(oxca)M(phen)2]ClO4-2H20, where phen=l,10-phenanthroline, M= Mn2+, Co2+, Ni2+,Cu2+,Zn2+. They have been characterized through the results obtained from elemental analysis, IR, electronic spectrum et al. The studies by cyclic voltammetry show that within the binuclear complexes "inner" Cu(II) is easy to reduct.The temperature dependence of the magnetic susceptibility of Cu(II)-Mn(II) and Cu(ir)-Ni(H) over the range 4 ~ 300K gave the exchange integral J= -10.56cm"1 and J= -17.08cm"1. It shows that when Cu(II) is under N3O coordination enviroment magnetic exchange interaction is smaller than under the N4 enviroment. Moreover , the change within Cu(II)-Ni(II) is more obvious. The reason is perhaps that O atom has higher electronegativity than N atom and then d-electron of Cu(II) has stronger delocalization.Using Na[Cu(oxca)] -l.SHaO as building block and adopting the strategy of "complexes as ligands" we have designed and synthesized and characterized five trinuclearcomplexes[CuCoxca)]2M-2H20 (M=Mn2\ Co2\ Ni2\ Cu2\ Zn2+) .The,studies by cyclic voltammetry show that within heterotrinuclears two Cu(II) have very different electrochemical behavior except [Cu(oxca)]2Zn-2H2O. The temperature dependence of the magnetic susceptibility of [Cu(oxca)]2Co-2H2O over the range 4 ~ 300K gave the exchange integral J= -28.09cm"1, g-2.13, F=3.81xlO"3.Using Na[Cu(oxca)] -l.SHiO as building block we have synthesized and characterized two rare earth-transition metal heterotetranuclear complexes [Cu(oxca)]3M(H2O)2-5H2O (M=Nd, Gd) . The electrochemical properties have been studied. The temperature dependence of the magnetic susceptibility of [Cu(oxca)]3Gd(H2O)2’5H2O over the range 4 ~ 300K gave the exchange integral J=0.537cm"1,g=1.955, F=5.68X 10~4. The smaller J value indicates that there is a very weak ferromagnetic spin exchange interaction between Cu+ and Gd3+ within heterotetranuclear complex. This may account for the fact that 4f-electrons are shielded by the outer shell electrons.更多还原