5-溴烟酸配合物和手性三联吡啶功能化合物的合成、表征与性能研究

发布时间：2018-03-14 13:38

本文选题：5-溴烟酸配体　切入点：金属-有机配位聚合物　出处：《郑州大学》2016年硕士论文　论文类型：学位论文

【摘要】：金属-有机配位聚合物骨架材料是一类具有潜在应用价值的新型材料。本论文以5-溴烟酸为主配体和具有磁性的金属离子Fe(II)、Ni(II)、Co(II)等组装合成了4个新颖的配位聚合物:[Fe(Br-a)2(H2O)2]n(1)、[Ni(Br-a)2]n(2)、[Ni(Br-a)(bpy)(H2O)2]n?n(Br-a)?4.5nH2O(3)和[Co2(Br-a)3(bpy)2(OH)]n?nH2O(4)[Br-a=5-溴烟酸,bpy=4,4'-联吡啶],系统地探讨了1-4的合成方法、结构和相关性质。在配合物1中,配体Br-a桥联金属离子Fe(II)形成折皱的层结构;相邻层之间通过O···Br弱作用叉合形成三维超分子网络结构。配合物2-4都含有由配体Br-a桥联的双核金属结构亚单元,但它们的结构却有明显的区别。配合物2是一个罕见的孪生配位聚合物,含有由孪生螺旋桨结构亚单元[Ni2(Br-a)4]构成的孪生(4,4)层结构。在化合物3中,辅助配体bpy桥联环状的双核结构单元[Ni2(Br-a)2]形成具有63拓扑结构的二维阳离子框架,游离的抗衡阴离子Br-a被捕获在它的纳米格子里。在配合物4中,辅助配体bpy桥联[Co2(Br-a)3(OH)]双核单元形成梯状的手性双链结构。特别值得一提的是,和卤素有关的弱相互作用对形成1-4的三维金属超分子结构起到了关键性的作用。对化合物1-4的热分析研究表明,这些聚合物骨架在270℃以下是稳定的。对化合物的2和4的磁性研究表明,化合物2表现出弱的反铁磁相互作用,主要是通过螺旋桨结构亚单元[Ni2(Br-a)4]中羧基桥进行磁交换;而化合物4表现出的较强的反铁磁相互作用,则是通过双核结构单元[Co2(Br-a)3(OH)]中羧基桥和羟基桥共同进行磁交换。三联吡啶是强的荧光发射团。因此,基于三联吡啶设计合成三联吡啶功能化合物在开发发光材料方面具有重要的意义。本论文设计合成了四个手性三联吡啶化合物,即(L)-三联吡啶苯甲基-丙氨酸酰肼[(L)-T~1]、(D)-三联吡啶苯甲基丙氨酸酰肼[(D)-T~2]、(L)-三联吡啶苯甲基-水杨醇基-丙氨酸酰腙[(L)-T~3]和(D)-三联吡啶苯甲基-水杨醇基-丙氨酸酰腙[(D)-T~4],并通过红外、核磁、高分辨质谱等确定了化合物结构。研究了它们的荧光和旋光性质。旋光性质测试表明(L)-T~1和(D)-T~2的比旋光度大小相等符号相反,是对映异构体;而它们和水杨醛缩合的酰腙化合物(L)-T~3和(D)-T~4都具有非常大的正比旋光度,是非对映异构体,除手性碳原子外,分子中衍生出了新的螺旋手性。特别有趣的是,由对映异构体(L)-T~1和(D)-T~2同水杨醛在完全相同的实验条件下缩合,得到的化合物(L)-T~3和(D)-T~4的结构完全不同,推测可能是由于手性碳的不同构型控制了有机反应的历程。荧光测试结果表明,化合物(L)-T~1、(D)-T~2、(L)-T~3和(D)-T~4在紫外-可见光范围内都具有强的荧光发射。化合物(L)-T~3和(D)-T~4都具有双波长荧光发射。特别是化合物(D)-T~3它的两个荧光发射峰的位置分别在456 nm和560 nm,为紫光和黄绿光,是一对互补色光,可以作为潜在的白光材料。
[Abstract]:The metal-organic coordination polymer skeleton material is a kind of new material with potential application value. In this paper, four novel coordination polymers [Fe(Br-a)2(H2O)2] nca1n, [Ni(Br-a)2] n2, [Ni(Br-a)(bpy)(H2O)2] n? Nbsp Br-aHU? 4.5n H _ 2O _ 3) and [Co _ 2H _ 2Br-a ~ (3) B _ pyY _ 2O _ H)] n? The synthesis, structure and properties of 1-4 were systematically discussed. In complex 1, the ligand Br-a bridged metal ion FeII formed a wrinkled layer structure. Three dimensional supramolecular networks are formed by the weak interaction of O 路路Br between adjacent layers. The complexes 2-4 contain binuclear metal structural subunits bridged by ligand Br-a. However, their structures are obviously different. Complex 2 is a rare twinning coordination polymer containing the twinning 4 (4) layer composed of twin propeller structural subunits [Ni2(Br-a)4]. In compound 3, An auxiliary ligand bpy bridged binuclear unit [Ni2(Br-a)2] forms a two-dimensional cationic frame with 63 topologies, and free countervailing anionic Br-a is trapped in its nano lattice. The auxiliary ligand bpy bridged [Co2OBr-aOH] binuclear units form a ladder of chiral double-stranded structures. The weak interaction associated with halogen plays a key role in the formation of a three-dimensional metallic supramolecular structure of 1-4. The thermal analysis of compounds 1-4 shows that, The magnetic properties of compound 2 and 4 show that compound 2 exhibits weak antiferromagnetic interaction, which is mainly exchanged by carboxyl bridge in propeller structural subunit [Ni2(Br-a)4]. On the other hand, compound 4 exhibits strong antiferromagnetic interaction through magnetic exchange between carboxyl and hydroxyl groups in the binuclear structure unit [Co2OBr-aH3OH]. The tripyridine is a strong fluorescent emitter. The synthesis of tripyridine functional compounds based on tripyridine has important significance in the development of luminescent materials. In this paper, four chiral tripyridine compounds were designed and synthesized. LPH-tripyridine-phenylmethyl-alanine hydrazide [LT1] dipyridyl phenylmethyl alanine hydrazide [DPMP] LPN-tripyridine-salicylidene-alanine acylhydrazone [LH3] and D- tripyridine-phenylmethyl-salicylidene-alanine acyl Hydrazone [DH4] were passed through IR, IR, IR, IR, IR, IR, IR, IR, IR, IR, IR, IR, IR, The structures of the compounds were determined by NMR and high resolution mass spectrometry. The fluorescence and optical properties of these compounds were studied. And the acylhydrazone compounds that are condensed with salicylic aldehydes---. From the condensation of the enantiomers of LX TX 1 and DX TX 2 with salicylic aldehyde under the same experimental conditions, the structures of the compounds, Ln TX 3 and DX TN 4, were completely different. It is speculated that the organic reaction is controlled by the different configurations of chiral carbon. The two compounds, L1, TX, DX, TX, and DX, have strong fluorescence emission in the range of UV and visible light, both of them have dual wavelength fluorescence emission. In particular, the position of two fluorescence emission peaks of compound DX TX 3 is at 456 nm and 560 nm, respectively, and the fluorescence emission peaks of the two compounds are at 456 nm and 560 nm, respectively, and the fluorescence emission peaks of the compounds are located at 456 nm and 560 nm, respectively, and the fluorescence emission peaks of the compounds are at 456 nm and 560 nm, respectively, and the fluorescence emission peaks of the compounds are at 456 nm and 560 nm, respectively. For the purple light and the yellow green light, Is a pair of complementary color light, can be used as a potential white light material.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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