新型多原子桥联多核配合物的合成、表征和磁性研究

【作者】 舒春英；

【导师】 石敬民；

【作者基本信息】 山东师范大学 ， 物理化学， 2000， 硕士

【摘要】 本文选用方酸根（Sq）、4，4’—联吡啶（Bpy）、硫氰酸根（SCN^-）、N，N’—双（N-丁基-乙基胺）草酰胺（H₂L）、氰根（CN^-）为多原子桥联配体，设计和合成了5个文献尚未报道的新型多原子桥联多核配合物。对所合成的配合物进行了元素分析和波谱表征。并对其中的4个配合物进行了变温磁化率和变温磁矩的测定，对所测数据进行了理论分析，得到了表征配合物中金属离子间磁相互作用强弱的磁交换积分J值。讨论了不同的端基配体和平衡离子对金属离子间磁相互作用的影响。测定了配合物[Ni₂（en）₄（SCN）₂]（ClO₄）₂和Cu₂L₄Fe（CN）₆（L为乙醇胺）的晶体结构。本研究丰富了多原子桥联多核配合物的内容，对探索多核类配合物在生命科学和材料科学中的作用机理和开发多核类配合物在该领域的实际应用具有一定的意义。 本研究的主要特点和贡献如下所述： 1、合成了方酸根桥联的新型双核Cu（Ⅱ）配合物[Cu₂（HNAQ）₂Sq]·3H₂O，并对其进行了变温磁化率的测定。探讨了端基配体对方酸根桥联双核Cu（Ⅱ）离子间磁相互作用的影向。 2、合成了端基配体为1-甲基-异羟丙基乙二胺（HL）的配合物[Cu₂（L）₂bpy]（ClO₄）₂·H₂O，测定了其变温磁化率，得到了表征配合物中金属离子间磁相互作用强弱的磁交换积分2J=-199.0cm^-1。目前文献报道的4，4’—联吡啶（Bpy）桥联的Cu（Ⅱ）-Cu（Ⅱ）双核配合物间的磁交换积分|2J|一般不大于3。本研究的发现对探索了解多原子桥联金属离子间的磁相互作用具有重要的理论及实验意义。 舒作帖 山尔Vll卜0人。刊凶I：毕业伦义0—— 3、合成了首例草即版类配体桥联双核 Ni门I川合物 压Ni2（L）（Phen）＊（H二O）月(CIO 小，得多了衣O配介物’－呸’太旭离厂丁 磁 相互作用强弱的磁交换积分刀—一32．3 cm‘，这比义献报迢的V 酞胺类配体桥峨的双核配合物的磁交换积分郴小，从而进一步证 实了配合物的共平面性与桥联朵属离了叫磁们止们川】＜仙杯在估 相关的内在联系，这为以后设计合成新型多核配介物只有重坐的 创沦及实验总义。 4、首次合成了CN－桥联异核过股十属离丁〔rJ ｛ tK网状纪构 配合物，得至了单品Cu！L司Fe（CN）o＊义其进千 了＊现性表b及电 子能谱测试，初步分析表明其中的铜离子与铁离了分别以个M的 价态存在于配合物中。本研究工作对于分丫铁磁体类配合物的介 成A有：川常重业的用！论及实验愈义。更多还原

【Abstract】 In this paper, Squarate(Sq) 4,4[3ipyridinc(Bpy) - Thiocyanato(SCN ) N,N3 is(Nutylthylcneam i nO oxamido and Cyanide(CN) have been selected as multitom bridge ligands. Five novel complexes have been designed and synthesized. The all complexes were characterized by elemental atialyses and conductance, UVisible spectra and IR. The temperature dependence of the magnetic susceptibilities and the magnetic moments for the four complexes were measured. The magnetic analyses were performed using the susceptibility equations based on the Heiscnberg spin? exchange operators and the magnetic parameters J that imply the magnitude and nature of magnetic interaction between the bridged metal ions have been obtained. The discussion was made on the factors that affect spinxchange interaction between the bridged metal ions. The factors include the different terminaligand and balance ions. The crystal structures of the complexes [Ni2(en)4(SCN)2j(C104)2 and 2Cu(L)2Fe(CN)6 have been determinated. The paper will provide the iicw content for the complexes that contain multitom bridgeigand and have a certain of meaning in the respects of exploring the mechanism of the magnetic interaction and using practically of these kinds of complexes in thc life science and the material science. The main characteristics and the contributions of the present paper are: I. The temperature dependence of the magnetic susceptibilities of the complexes (Cu2(HNAQ)2 Sq] 31120 was measured (I INAQ = Hydroxyl aphthaldehyde-8-amino uinoline),demonstrating that different Shiffases as capped ligand have little cflts on the magnetic interaction between the bridged metallic ions. The present result will provide experimental data and important theoritical reference for exploring the mechanism of magnetic interaction between the bridged metallic ions. 2. The complex [Cu2( L)2bpyj (dO4) 2 1120 (I. as terminal ligand and HL N(2ydroxypropyl) ,2ropylcncdiamine) was synthesized. The complex demonstrates the strong magnetic interaction (2J = 99.0 cnf. According to our best knowledge, the magnetic exchange integral 12J1 between Cu( II) u( II) ions bridged by 4,4ipyridine is no larger than 3 cm The present result will have important theoritical meaning in exploring the mechanism of magnetic interaction between bridged transition metallic ions. 3. The complex [Ni2(L)(Phcn)2(l1,0)j(Cl04)2 (L = oxamido,N is(Nutylthyleneamine), phen = 1,1 0henanthroline) was synthesized. The magnetic coupling parameter between Ni( II) Ni( II) was obtained (2J = 2.3 cm,which is smaller(absolute value)than that of the other complexes with the oxamido as the bridged ligand. he main factor is that the present bridging ligand has more bulky substituent, i.e. the Nutyl, which must cause the lower colane of the complex and the smaller overlap of the magnetic orbitals. And this in turn leads the weaker magnetic interaction. 4.The complex Cu2L4Fe(CN)6 was synthesized, which may be thefirst complex that have a three-dimensional structure with the CN asthe bridged ligand. The complex was charactered by tl1e IR spectraand the crystal structure was charactered by X-Ray po’vcr diffractionand XPS. This work will have an important meanil1g il1 the respcctof the molecular ferromagnet.更多还原