氰根、叠氮桥连的双稳态分子磁性材料构筑及性能研究

RESEARCH ON BISTABLE COORDINATION POLYMERIZATION MAGNETIC MATERIAL BASED ON CYANIDE AND AZIDE BRIDGE

杨炅

11649074

硕士

化学

张元竹

2018

2018.7.6

哈尔滨工业大学

深圳

分子磁性材料主要是由金属离子和有机小分子桥配位键连而成，辅以有机配体加以结构调控，通过“分子工程”的组装方法发展起来的一类具有特定磁学功能的新型分子材料。近年来， 分子 磁性材料， 尤其是单分子磁体和单链磁体的研究受到了国际化学工作者广泛的关注，而如何解决好在优化磁各向异性的同时增加分子自旋态是单分子磁体 、 单链磁体的 一个 挑战 。 本论文 通过原子替代和 “brick and mortar”等原则实现对目标分子的定向合成和结构调整 用二核或四核等具有较高自旋态的簇合物去取代 Ni(II)金属离子 ，在优化其磁各向异性的前提下提升分子磁体的自旋基态，以 期 获得具有更高能垒或更大阻塞温度的分子磁体。以[(TpR)FeIII(CN) 为 构筑基元， 利用 叠氮 EO桥连 来传递 Ni(II)离子间 耦合 作用， 参照 化合物 FeIII2NiII用 [Ni2(bpp)2(N3)2]取代 Ni(II)离子我们得到了 化合物[Ni2(bpp)2(N3)2][pzTpFe(CN)3]2∙H2O (1)和 [Ni2(bpp)2(N3)2][Tp*MeFe(CN)3]2. H2O (bpp = 2,6–di(1H–pyrazol–1–yl)pyridine) ( 用 Ni4簇合物 (Ni4 : [Ni4L2(MeO)2(N3)2(DMF)2])作为前驱体 我们得到了 化合物 {[Ni4L12(MeO)2 -(N3)2(DMF)2][TpFe(CN)3]2} .DMF (L-1 = 1,1'–(((1E,1'E)–(2–hydroxy–5–methyl–1,3–phenylene)bis(methanylylidene))bis(azanylylidene))bis(propan–2–ol)) (3)。 我们还获得了 基于 [Ni2(enbzp)(N3)2]构筑 基元的 化合物 [Ni4(enbzp)2(N3)4][Tp*Fe(CN)3]4.2DMF (enbzp = (1E,1'E)–N,N'–(ethane–1,2–diyl)bis(1–phenyl–1–(pyridin–2–yl)methanimine)) (4)和基于 [Ni3(enbzp1)2(N3)4]结基元 的化合物{[Ni3(enbzp1)2(N3)4][pzTpFe(CN)3]2}n (enbzp1 = (E)–2–((phenyl(pyridin–2–yl)methyl -ene)amino)ethan– 1–amine) ( 并进行了结构和磁性分析 。此外通过FeCl2·6H2O CoCl2.6H2O分别 与 叠氮 、 bzp的组装得到链状化合物[(bzp)Fe(μ1,1–N3)2]n (6)和 [(bzp)Co(μ1,1–N3)2]n ( 且配合物 6和 7均表现出 单链磁体行为。

Molecular magnetic materials are mainly composed of metal ions coordinated with organic molecule bridges, supplemented by organic ligands for structural regulation, and a new class of molecules with specific magnetic functions developed through the "molecular engineering" assembly method.In recent years, the research of molecular magnetic materials, especially Single-Molecule Magnets(SMMs) and Single-Chain Magnets(SCMs), has received extensive attention from international chemical workers.How to solve the problem of optimizing the magnetic anisotropy while increasing the molecular spin state in SMMs or SCMs are a challenge.In this dissertation, directional synthesis and structure adjustment of target molecules are achieved by the principles of atom substitution and "brick and mortar", and NiII metal ions are replaced by clusters with higher spin states such as dinuclear or tetranuclear. The magnetic anisotropy enhances the spin ground state of the molecular magnets in order to obtain molecular magnets with higher energy barriers or larger blocking temperatures.Using[(TpR)FeIII(CN) as the building block, the NiII ion coupling effect is transferred by the azide EO bridging, and the reference compound FeIII2NiII replaces Ni with [Ni2(bpp)2(N3)2] cluster we got compounds [Ni2(bpp)2(N3)2][pzTpFe(CN)3]2∙H2O (1) and [Ni2(bpp)2(N3)2][Tp*MeFe(CN)3]2. H2O (bpp = 2, 6–di(1H–pyrazol–1–yl)pyridine) (Using Ni4 cluster (Ni4 : [Ni4L2(MeO)2(N3)2(DMF)2]) as a precursor we obtained the compound {[Ni4L-12(MeO)2 -(N3)2(DMF)2][TpFe(CN)3]2}.DMF (L-1 = 1,1'–(((1E,1'E)–(2–hydroxy–5–methyl–1,3–phenylene)bis(methanylylidene))bis (azanylylidene))bis (propan–2–ol)) (3) .We also obtained the compound [Ni4(enbzp)2(N3)4][Tp*Fe(CN)3]4. 2DMF (enbzp = (1E,1'E)–N,N'–(ethane–1,2–diyl)bis(1–phenyl–1–(pyridin–2–yl) methanimine)) (4) based on the [Ni2(enbzp)(N3)2] construction motif; and based on [Ni3(enbzp1)2(N3)4] Structural motif of the compound {[Ni3(enbzp1)2(N3)4] [pzTpFe(CN)3]2}n (enbzp1 = (E)–2–((phenyl(pyridin–2–yl)methyl -ene)amino)ethan– 1–amine) (5).In addition, the chain compounds[(bzp)Fe(μ1,1–N3)2]n (6)和 [(bzp)Co(μ1,1–N3)2]n (7) are obtained through the assembly of FeCl2·6H2O and CoCl2.6H2O with azide and bzp, respectively, and both complexes 6 and 7 exhibit single-chain magnet behavior.

单分子磁体 单链磁体 氰根 叠氮

single–molecule magnet single–chain magnet cyanide azide

中文

联合培养

南方科技大学

杨炅. 氰根、叠氮桥连的双稳态分子磁性材料构筑及性能研究[D]. 深圳. 哈尔滨工业大学,2018.