摘要
近三十多年来,配位化合物的磁学性质研究一直是磁性材料领域的前沿学科之一。大量的含有自旋载体的多核配合物已被合成,这些已报道的配合物其自旋载体间主要由单原子桥联配体和多原子桥联配体所联接。只有为数极少的一些自旋载体配合物间是经分子间力所维系。从这些配合物的磁学性质研究中,一些主导磁耦合性质的关联因素已被相关研究者所认知。但是,人类远未了解自旋载体间磁耦合的机理,以致还未能设计合成理想的分子基铁磁材料。因此,设计合成新型配位化合物,特别是自旋载体间经分子间力维系的多核配合物则具有非常重要的理论与实验指导意义。基于此,本论文共涉及合成了6个新型配合物,这包括三个含有2-甲氧基-1,10-邻菲啰啉化合物（L1)为配体的配合物,即以羟基和叠氮酸根为混合桥联配体和2-甲氧基-1,10-邻菲啰啉化合物为端接配体的四核Cu(II)配合物[Cu_4(μ-OH)__2(μ-N_3)___2(H_2O)__2(Phen-OCH_3)_4](ClO_4)4 (1);以氯离子为桥联配体、2-甲氧基-1,10-邻菲啰啉和氯离子为端接配体的双核Cu(II)配合物[Cu__2(μ-Cl)2(Phen-OCH_3)(Cl_2(] (2)和以2-甲氧基-1,10-邻菲啰啉、硫氢酸根和甲醇均为端接配体的单核Mn(II)配合物[Mn(Phen-OCH_3)___2(HOCH_3)(NCS)](ClO_4) (3);另外三个新型配合物为以2-(1,2,4-三唑)-1,10-邻菲啰啉化合物为端接配体的单核Cu(II)配合物[Cu(TP)2]?2BF4?CH_3CH_2OH (TP = 2-(1H-1,2,4-triazol-1-yl)-1,10-phenanthroline) (4),以2-乙氧基-1,10-邻菲啰啉和叠氮酸根为桥联配体的单核Cu(II)配合物[Cu(Phen-OCH_2CH_3)___2(N_3)]2H_2O(5)和以2,9-双(3,5-二甲基吡唑)-1,10-邻菲啰啉、亚硝酸根和甲醇分子为端接配体的单核Cd(II)配合物[Cd(DPP)(OON)OHCH_3]ClO_4 (DPP = 2,9-bis(3,5-dimethyl-1H-pyrazol-yl-1)-1,10- phenanthroline) (6)。
对所合成的配合物进行了红外光谱和X-射线单晶衍射结构表征。对配合物(1)进行了量化计算并获得了各个磁耦合通道所导致的磁耦合性质,并就其磁学性质与结构间的关联因素进行研究;测定了配合物(2)的变温磁化率数据,并对其进行了拟合处理从而获得了该配合物的实验磁耦合性质,使用量化计算方法研究了该配合物桥联磁耦合通道,π?π重叠磁耦合通道和非经典氢键磁耦合通道所导致的磁耦合性质,从而合理解释了由实验所得的磁耦合性质。对配合物(3),(4)和(5)结构所示的分子间相互作用力所形成的磁耦合通道的磁耦合性质进行了量化计算,研究了其结构与磁耦合性质间存在的构效关联因素。
本论文的研究成果对于更进一步探索了解以氯离子为桥联配体、以叠氮酸根和羟基为混合桥联配体的多核配合物的磁耦合性质,以及探索了解由分子间力所导致的磁耦合性质方面具有十分重要的理论与实验指导意义。同时,该论文的研究成功对于设计合成理想的分子基铁磁材料方面也具有重要的理论与实验指导意义。
For more than three decades, the study of magnetic properties for complexes has been one of advanced disciplines in magnetic materials. A large number of multi-nuclear complexes have been synthesized and for these complexes the spin-carriers were linked by mono-atom or multi-atoms bridge ligands, and only a limited complexes deal with spin-carriers being connected by intermolecular force. Based on the study on these complexes some factors that dominate magnetic coupling properties have been understood. But it is far from to understanding thoroughly the relevant magnetic coupling mechanism and no ideal molecule-based ferromagnet has been synthesized to date. Therefore, it is very important in both the theory and the experiment area to design and synthesize new complexes, especially for the multi-nuclear complexes that the spin-carriers were linked by intermolecular force. Based on the concept mentioned above the six novel complexes have been designed and prepared, in which it includes three complexes with 2-methoxy-1,10-phenanthroline as one of terminal ligand, namely, the tetra-nuclear Cu(II) complex [Cu4(μ-OH)__2(μ-N_3)__2(H_2O)__2(Phen-OCH_3)_4](ClO_4)4 (1) with hydroxyl anion and azide anion as mixed bridge ligand and 2-methoxy-1,10-phenanthroline as terminal ligand; binuclear Cu(II) complex [Cu__2(μ-Cl)__2(Phen-OCH_3)(Cl)_2] (2) with two chlorido anions as bridge ligand and another two chlorido anions and 2-methoxy-1,10-phenanthroline as capped ligands; mono-nuclear Mn(II) complex [Mn(Phen-OCH_3)__2(HOCH_3)(NCS)](ClO_4) (3) with 2-methoxy-1,10 -phenanthroline, thiocyanate anion and methanol as terminal ligand. Another three novel complexes involve the mono-nuclear Cu(II) complex [Cu(TP)_2]?2BF4?CH_3CH_2OH (TP = 2-(1H-1,2,4-triazol-1-yl)-1,10- phenanthroline) (4) with 2-(1H-1,2,4-triazol-1-yl)-1,10-phenanthroline as terminal ligand; the mono-nuclear Cu(II) complex [Cu(Phen-OCH_2CH_3)__2(N_3)]2H_2O (5) with 2-ethoxyl-1,10-phenanthroline and azide anion as terminal ligands; mono-nuclear Cd(II) complex [Cd(DPP)(OON)OHCH_3]ClO_4 (DPP = 2,9-bis(3,5-dimethyl-1H-pyrazol-yl-1)-1,10-phenanthroline)(6) with 2,9-bis(3,5- dimethyl-1H-pyrazol-yl-1)-1,10- phenanthroline, nitrite anion and methanol as terminal ligands.
For the complexes the infrared spectrum characterization was performed and their crystal structures determined with X-ray crystallography. The theoretical calculations were performed on complex (1) and based on the data of the calculations it is known that the magnetic coupling pathway of both hydroxyl anion and azide anion as bridge ligands results in strong ferromagnetic interaction, whereas another three magnetic coupling pathways only lead to the weak ferromagnetic coupling and the weak anti-ferromagnetic coupling, respectively. The variable-temperature magnetic susceptibility was measured for complex (3) and the fitting for the variable-temperature magnetic susceptibility reveals that there are a medium ferromagnetic interaction and a weak anti-ferromagnetic interaction among the adjacent Cu(II) ions. The theoretical calculations indicate that the magnetic coupling pathway of the chlorido anion as bridging ligand brings about medium ferromagnetic coupling, theπ?πstacking pathway results in a weak ferromagnetic interaction. The other three magnetic coupling pathways from the Cl???H short contact lead to the weak anti-ferromagnetic interaction. Obviously, the ferromagnetic coupling from the experimental fitting seems from the cooperation of the magnetic coupling pathway of the chlorido anions as bridging ligand and theπ?πstacking pathway; whereas the anti-ferromagnetic coupling of the fitting may arise from the cooperation of the three magnetic coupling pathways of the Cl???H short contact .The theoretical calculations accord basically with the experimental fitting. The theoretical calculations also gave the information of the magnetic coupling properties dealing with the relevant coupling pathways in complex (3), complex (4) and complex (5), and the correlation between the relevant structural factors and the magnetic coupling properties were studied and the some interesting information was obtained.
The obtained results from the dissertation will not only benefit to further understanding the magnetic coupling properties of the complexes with chlorido anion as bridge ligand and the complexes with anzide anion and hydroxyl anion as mixed bridge ligands and but also it will benefit to understand the magnetic coupling properties arisen from the intermolecular force. At the same time, the dissertation may benefit to design and synthesize the ideal molecule-based ferromagnets.
引文
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