功能配合物的合成及相关性能研究

【作者】 胡春霞；

【导师】 李延团；

【作者基本信息】 曲阜师范大学 ， 无机化学， 2001， 硕士

【摘要】 本研究课题以磁性分子设计为主线，定向合成了一系列目标单、多核配合物，运用元素分析、红外、电导等手段进行了表征。使用磁天平，提拉样品磁强度计测定配合物的室温磁化率和变温（4-300K）磁化强度。运用配位场、分子轨道等近代量子化学方法、配合微机计算注释各种波谱数据，推定配合物的结构及自旋磁交换作用的大小和品质。从理论和实验两个不同角度全面系统地研究了功能配合物的磁性、生物活性、以及热分解动力学，建立起这些体系中物质的结构与性能的关系，进而为分子磁工程和晶体工程提供理论依据，开辟了多核配合物在生物领域应用的新途径。 1、以均苯四甲酸根（PMTA）为桥联配体，分别端接乙二胺（en），1,2-丙二胺（ap）和1,3-丙二胺（pn），合成和表征了三种均苯四甲酸根桥联的新型双核铜（Ⅱ）配合物，其配位反应可表示为： PMTA2-+2Cu’—+2L 一[Cu：（PMTA）L：]” （L‘en，ap，pn） 应用元素分析、摩尔电导、IR和电子光谱等方法，推定了配合物的组成和结构，测定和解析了配合物[Cu₂（PMTA）（en）₂]（ClO₄）₂的变温磁化率，求得磁参数为j=-0.88cm^-1,g=2.12。结果表明，该双核配合物中Cu（Ⅱ）离子间存在弱的反铁磁性自旋交换相互作用。研究了配体及目标配合物对几种常见菌株的抗菌活性。结果表明，这些配合物均有一定的抗菌活性。 2、以氯冉酸根（CA）为桥联配体，分别端接5-苯基-1，10-邻菲罗啉（ph-phen），乙二胺（en）和1,3-丙二胺（pn），合成和表征了三种新的双核铬（Ⅲ）配合物，其配位反应可表示为： CA)-2Cr’”+4l一[Cr，（CA）L，]… 曲阜师范大学硕士学位论文 队一吵－Phen，en，Pn) 推定配合物具有氯冉酸双核结构，其中每个铬皿)离子处于 八面体环境。测定了配合物＊r。K幻O卜吵＊川侣4)。的变温磁化 率，其数据与自旋哈密顿算符H＝－ZJS；l。导出的磁方程拟合， 求得交换积分为卜习．15 cm－’，g二2刀5。表明配合物中两个铬（Ill） 离于之间存在弱的反铁磁性自旋交换作用。 3、以配合物配体 凡N’－双（3－氨基－2，》二甲丙基）草酚胺合 铜（11）［Cu（M。OXpfl）二与 Cr”O。)二．gH。O反应，分另端接 5一甲基一 1，10－邻菲罗琳（MePhen），4，7－二苯基－l，10－邻菲罗琳（Ph，Phed） 和2，2’一二联毗唆（加仆 合成和表征了三千新的 h（1）－O（11！）异 双核配合物，其配位反应可表示为： Cu（Me。oxPn）－C／”－ZL一［Cu（Me。oxPn）Cr（L）。］”” （L—MePhen，Ph。Phen，bPy）．推测 了配合物的结构与组成，测定和解析 了 KLI（MC，OXPtt）Cf（Ph、）】仰O。）。（l）和KU仰C，OXPfl)C州CPhCll)，1wO。)。（2）们 变温磁化率，得门)、（2的磁参数分另为＊一ZI．5 CCI‘（l），J．二 22．8 cm－‘（2）。结果表明异双核配合物中，Cu且）和＊ 互离子间 存在铁磁性自旋交换相互作用。 4、应用TG－DTG－DTA热分析技术研究了配合物N，N”－双o－氨乙 基)草酚女合铜(卜 ICu（oxae）·H〕O仰 N，N’一双(3一氨丙某草臼时 合铜门1Hu…xpn刁在空气中的热稳定性，用微分法和积分法协 同处理非等温TG数据，通过对比热分解动力学参数 E和 InA， 提出了【Cu(oxae·HD」和【Cu（oxpn）」的热分解反应机理，并由动力 学补偿效应获得了E 与 ＊ 的数学表达式。研究发现配合物 r。。（OOpll）。热走定忏高于KLI（OXXX）·H，O〕。更多还原

【Abstract】 The design, synthesis and characterization of a series of target complexes, as a basis of this paper, focus on systematically dealing with the magnetic properties, biological activities and the thermal decomposition kinetics of them, according to the main routes of designing magnetic molecules.1. Three new u-tetracarboxylatobenzene binuclear copper( II) complexes have been synthesized and characterized. The general synthetic pathway for the complexationon may be represented by the following equationThe results have confirmed that the complexes have tetracarboxylatobenzene-bridged structures consisting of planar copper( II) ions. The temperature dependence of magnetic susceptibilities of the complex [Cu2(PMTA)(en)2](ClO4), was measured and analyzed over the range 4-300K, the antibacterial activity of these three complexes were also examined , demonstrating that there is a very weakly antiferromagnetic spin-exchange interaction between the two copper( II) ions within each molecule, and the antibacterial activities of all the binuclear complexes are superior to the ligand.2. Three new chloranilato-bridged chromium (Ill)-chromium (III) binuclear complexes have been synthesized and characterized. The reaction may be expressed as the following equation:Based on elemental analyses, IR electronic specteral, molar conductance, room temperature magnetic moment and variable temperature magnetic susceptibility(4-300K) measurements, these complexes are proposed to have chloranilato-bridged structures consisting of octahedral chromium(III) ions. The variable temperature magnetic susceptibilities (4-300K) of complex [Cr:(CA)-(ph-phen)J(SO4), was further measured and studied, demonstrating the anti-ferromagnetic interaction between the adjacent two chromium( II) ions. the exchange integrals ( J ) were evaluated as -3.15cm1.3. Three new n -oxamido-bridged heterobinuclear copper ( 11 ) complexes have been synthesized and characterized. The reaction can be expressed just as the following equation:It is proposed that these complexes have oxamido-bridged structures consisting of planar copper(II) and octahedral chromium (III) ions. The variable temperature, magnetic susceptibilities (4-3OOK) of complexes [Cu(Me:oxpn)Cr(Mephen)2](NO3)5 (1) and [Cu(Me2oxpn)Cr(Mephen)-,](NO3)-; (2) were further measured, demonstrating the ferromagnetic interaction between the adjacent chromium(III) and copper( II) ions through the oxamido-bridge. Basedon the spin Hamiltanian operation, H = -2 JS, 5\ , the exchangeintegrals (J) were evaluated as +21.5 cm for (1) and +22.8 cm1 for (2).4. The thermal decomposition of N, N-bis(2-aminoethyI)-CKamido-copper (II) complex under dynamic air atmosphere was studied by TG. DTG and DTA techniques. The nonisothermal kinetics data were analvzed bv means of the Achar method and the Coats-Redfen method.The most probable kinetic model function was suggested, by comparison of the kinetic parameters. The mathematical expressions of E and InA were derived from the kinetic compensation effects.In this paper, elemental analyses, IR electronic spectral, molar conductance, room temperature magnetic moment and variable temperature magnetic susceptibility (4-3 00K) measurements have been used to characterize the complexes synthesized through various means. Based on the coordinate field theory and molecular orbital theory’ and quantum chemical methods, the structures , the quantity and the quality of the spine exchange interaction of the complexes have been proposed. Biological activities and the thermal decomposition kinetics have also been studied.更多还原