以氮芳香杂环类和硫氰酸根为配体的配合物的合成、表征及性质研究
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摘要
本论文设计合成了以硫氰酸根为桥联配体,4-硝基吡啶氮氧化物为端接配体的一维双核链式结构配合物[Co(μ1,3?NCS)2(NPDO)2]n (1)和[Mn(μ1,3?NCS)2(NPDO)2]n (2)。
设计合成了以3,3’-二胺基- 2,2’-联吡啶为配体的系列单核配合物[Mn(C10H10N4)3](NO3)2 (3),[Ni(C10H10N4)3](NO3)2 (4),[Cd(C10H10N4)3](NO3)2 (5)和[Zn(C10H10N4)3](NO3)2 (6);单核配合物[Cu(C10H4N3)Cl2] (7)和[Cu(C10H4N3)(SCN)2] (8)。对所合成的这八个新型多原子配合物进行了红外光谱表征,使用X-射线单晶衍射法分析测定了其晶体结构,并对配合物(1),(2)在4-300 K间进行了变温磁化率的测定。为了获得配合物(2)中桥联Mn(II)离子间磁耦合强度的信息,我们使用均匀一维桥联Mn(II)链式拟合公式对所得实验磁化率数据进行了拟合处理,得到其磁耦合常数2J = ? 2.50 cm?1。同时使用相关结构参数分析配合物(1),(2)的磁学性质。另外,我们分析了以3,3’-二胺基-2,2’-联吡啶为配体的各个配合物的结构特点。
本论文将有助于芳香族氮氧化合物类配合物的合成及磁学性质研究,对于设计、合成以联吡啶衍生物类为配体的新型配合物也具有重要的理论和实验指导意义。
In this dissertation 4-nitropyridine N-oxide (NPDO) and thiocyanate have been selected as ligands and two novel complexes with thiocyanate as bridging ligand have been designed and synthesized, namely, the one-dimensional chain coordination polymers [Co(μ1,3?NCS)2(NPDO)2]n (1) and [Mn(μ1,3?NCS)2(NPDO)2]n (2).
In addition, 3,3’-diamino-2,2’-bipydine has been synthesized and selected as ligand and six novel complexes have been synthesized, namely, [Mn(C10H10N4)3](NO3)2 (3), [Ni(C10H10N4)3](NO3)2 (4),[Cd(C10H10N4)3](NO3)2 (5),[Zn(C10H10N4)3](NO3)2 (6), [Cu (C10H4N3)Cl2] (7) and [Cu(C10H4N3)(SCN)2] (8).
The eight novel complexes were characterized by IR spectra, and their crystal structures were determined by X-ray crystallography. The variable-temperature magnetic susceptibilities (4?300 K) of complexes (1) and (2) were measured. For the one-dimensional chain Mn(II) complex an uniform one-dimensional chain fitting formula was used and the magnetic coupling constant 2J = ? 2.50 cm?1 was obtained through fitting; the magnetic behaviors of both the complex (1) and (2) were analyzed with their structural factors. For the complexes dealing with 3,3’-diamino-2,2’-bipyridine as ligand, their structural characters were studied, respectively.
The dissertation will benefit the synthesis of aromatic N-oxide complexes and the magnetic studies of relevant complexes; and the important contribution of the dissertation lies in that it will benefit design and synthesis of the novel complexes with the derivatives of bipyridine as ligands.
设计合成了以3,3’-二胺基- 2,2’-联吡啶为配体的系列单核配合物[Mn(C10H10N4)3](NO3)2 (3),[Ni(C10H10N4)3](NO3)2 (4),[Cd(C10H10N4)3](NO3)2 (5)和[Zn(C10H10N4)3](NO3)2 (6);单核配合物[Cu(C10H4N3)Cl2] (7)和[Cu(C10H4N3)(SCN)2] (8)。对所合成的这八个新型多原子配合物进行了红外光谱表征,使用X-射线单晶衍射法分析测定了其晶体结构,并对配合物(1),(2)在4-300 K间进行了变温磁化率的测定。为了获得配合物(2)中桥联Mn(II)离子间磁耦合强度的信息,我们使用均匀一维桥联Mn(II)链式拟合公式对所得实验磁化率数据进行了拟合处理,得到其磁耦合常数2J = ? 2.50 cm?1。同时使用相关结构参数分析配合物(1),(2)的磁学性质。另外,我们分析了以3,3’-二胺基-2,2’-联吡啶为配体的各个配合物的结构特点。
本论文将有助于芳香族氮氧化合物类配合物的合成及磁学性质研究,对于设计、合成以联吡啶衍生物类为配体的新型配合物也具有重要的理论和实验指导意义。
In this dissertation 4-nitropyridine N-oxide (NPDO) and thiocyanate have been selected as ligands and two novel complexes with thiocyanate as bridging ligand have been designed and synthesized, namely, the one-dimensional chain coordination polymers [Co(μ1,3?NCS)2(NPDO)2]n (1) and [Mn(μ1,3?NCS)2(NPDO)2]n (2).
In addition, 3,3’-diamino-2,2’-bipydine has been synthesized and selected as ligand and six novel complexes have been synthesized, namely, [Mn(C10H10N4)3](NO3)2 (3), [Ni(C10H10N4)3](NO3)2 (4),[Cd(C10H10N4)3](NO3)2 (5),[Zn(C10H10N4)3](NO3)2 (6), [Cu (C10H4N3)Cl2] (7) and [Cu(C10H4N3)(SCN)2] (8).
The eight novel complexes were characterized by IR spectra, and their crystal structures were determined by X-ray crystallography. The variable-temperature magnetic susceptibilities (4?300 K) of complexes (1) and (2) were measured. For the one-dimensional chain Mn(II) complex an uniform one-dimensional chain fitting formula was used and the magnetic coupling constant 2J = ? 2.50 cm?1 was obtained through fitting; the magnetic behaviors of both the complex (1) and (2) were analyzed with their structural factors. For the complexes dealing with 3,3’-diamino-2,2’-bipyridine as ligand, their structural characters were studied, respectively.
The dissertation will benefit the synthesis of aromatic N-oxide complexes and the magnetic studies of relevant complexes; and the important contribution of the dissertation lies in that it will benefit design and synthesis of the novel complexes with the derivatives of bipyridine as ligands.
引文
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