【作者】 唐宽镇；

【导师】 唐瑜； 刘伟生；

【作者基本信息】 兰州大学 ， 无机化学， 2008， 博士

【摘要】 多足配体与金属离子配位时,能够表现出特有的选择性配位能力、类球形配位空穴和新颖的配位结构,从而成为近年来配位化学的研究热点。稀土离子具有独特的电子结构和成键特征,配位数高且多变,使得具有光、电、磁功能的稀土超分子配合物的组装成为一个具有挑战性的课题。众多已在功能超分子化学中表现出潜在应用前景的多足配体中,酰胺型多足配体在制备具有强荧光性质的稀土配合物中表现得尤其引人注目。此类多足配体具有合成简单、结构可调和共轭敏化基团可换等优点。通过调整配体的功能基团可以实现配合物优良的荧光性质。为了进一步研究和探讨酰胺型多足配体对稀土离子的配位选择性以及配体骨架结构、功能末端基和抗衡阴离子对配合物荧光性质的影响,本论文报道了酰胺型多足配体L~Ⅰ～L~Ⅸ及其稀土超分子配合物的合成与表征,并对配合物的荧光性质进行了比较系统的研究。稀土配合物的光、热和化学稳定性较差,限制了其在很多领域的实际应用,而无机基质材料大多具有良好的光、热和化学稳定性。因此,将二者复合,是改善稀土配合物的发光性能和光、热和化学稳定性、开发新型稀土发光材料、拓宽稀土发光配合物应用领域的新途径。本论文将酰胺型多足配体稀土配合物插层组装到蒙脱土的层板间,制备出具有层柱状结构的稀土配合物-蒙脱土超分子复合发光材料,复合材料的发光性能和光、化学稳定性较相应纯稀土配合物有显著改善。本论文共分六章:第一章:简要综述了近年来多足配体超分子配合物、稀土发光配合物和蒙脱土复合材料的研究进展。第二章:以乙酰苄胺和乙酰苯胺为功能末端基合成出两个具有相同柔性骨架的三足配体L~Ⅰ和L~Ⅱ,并合成了五种阴离子稀土盐的10个系列共65个稀土配合物。研究结果表明配合物均为双帽型稀土有机配阳离子结构。对配合物的超分子结构进行了深入研究,探讨了不同阴离子对配合物结构的影响以及分子间氢键、π-π堆积在构筑新颖超分子结构中的作用。第三章:以乙酰苄胺为功能末端基合成出四个具有不同刚性骨架的多足配体L~Ⅲ～L~Ⅵ,并合成了4个系列共28个稀土苦味酸盐配合物。配合物的晶体结构研究表明,配体L~Ⅲ、L~Ⅳ均能与稀土苦味酸盐形成1:1(M:L)型配合物,三个苦味酸根离子均参与配位,有效地保护了中心稀土离子,使其免受环境影响,有望获得发光性能优良的稀土功能配合物。第四章:以水杨酰苄胺和(间)水杨酰胺甲基吡啶为功能末端基合成出三个刚性骨架的多足桥联配体L~Ⅶ～L~Ⅸ,并合成出配体与稀土硝酸盐、稀土高氯酸盐的6个系列共31个配合物。晶体结构研究表明,配体L~Ⅶ、L~Ⅷ稀土硝酸盐配合物分别为多足配体稀土配合物中非常少见的(6,3)蜂巢状和(10,3)-a型配位聚合结构。第五章:对铕、铽配合物进行了荧光性质研究。结果表明,所有末端基对稀土离子均具有良好的敏化作用。配体的骨架结构、侧链数目和功能末端基以及抗衡阴离子对稀土配合物的荧光强度均产生一定影响。第六章:以第二章合成出的配体L~Ⅰ、L~Ⅱ的铕/铽配合物为原料制备出蒙脱土复合发光材料,用元素分析、XRD和IR对其进行了表征,并对复合材料的荧光性质进行了初步研究。结果表明,三足配体稀土有机配阳离子可通过室温溶液离子交换反应插层组装到蒙脱土的层板间,主-客体间以超分子作用力(此处主要是静电作用)结合成具有规整层柱结构的复合材料。复合材料较纯化合物有着更好的光、化学稳定性。本论文涉及到的配体:L~Ⅰ:2,2’,2”-胺三乙酰苄胺L~Ⅱ:2,2’,2”-胺三乙酰苯胺L~Ⅲ:三甘酰双苄胺L~Ⅳ:2,2’-(1,2-苯双氧代)双乙酰苄胺L~Ⅴ:2,2’-(1,2-萘双氧代)双乙酰苄胺L~Ⅵ:2,2’,2”-(1,2,3-苯三氧代)双乙酰苄胺L~Ⅶ:1,4-二[(2’-苄胺甲酰基苯氧基)-甲基]-2,5-二甲苯L~Ⅷ:1,3,5-三[(2’-苄胺甲酰基苯氧基)-甲基]苯L~Ⅸ:1,4-二{[2’-(3-吡啶甲胺甲酰基苯氧基)]-甲基}-2,5-二甲苯更多还原

【Abstract】 Podand-type ligands have drawn much attention in recent years,mainly due to their particular selective coordinating capacity,spheroidal cavities,and novel coordinational structure when they coordinate with metal ions.Rare earth elements are a group of special inorganic ions with good luminescent,electronic and magnetic properties.Among these podands having potential applications in functional supramolecular chemistry,amide-type podands have drawn much attention in preparing rare earth complexes with strongly luminescent properties. Amide-type podand ligands have the advantages in simple synthesis,adjustable structure and changeable sensitive conjugate groups,which make their complexes indicating good luminescent properties.In order to investigate the coordination properties of the amide-type podand ligands with rare earth ions,and the influence of different skeleton and the functional terminal groups of the ligands and different anions to luminescent properties of the rare earth complexes,this dissertation reported the synthesis and characterization of amide-type podand ligands L~Ⅰ～L~Ⅸ. The luminescent properties of the complexes have also been comprehensively investigated.The application of the rare earth complexes are limited by the poor optical,thermal and chemical stabilities.Stable inorganic solid matrices which can change the structure and chemical microenvironment of guest molecules or ions, could affect the luminescent properties of guest molecules or ions distinctly.So the hybrid of the rare earth organic complexes with suitable inorganic solid matrices is a desirable way to improve the luminescent properties and the stabilities of the complexes,develop novel rare earth luminescent materials and widen their application field.We intercalate rare earth luminescent complexes with amide-type podands into the interlayer space of montmorillonite(MT)and obtain novel rare earth complex-MT supramolecular composite luminescent materials which have better luminescence properties,better chemical and optical stabilities compared with their pure complexes.The dissertation includes following six chapters:1.A brief review of investigation progress of podand ligands supramolecular complexes,rare earth luminescent complexes and composite montmorillonite materials were summarized.2.Two same flexible framework of tripodal ligands L~Ⅰand L~Ⅱusing [N-(phenylmethyl)]acetamide and(N-phenyl)acetamide as terminal groups and 65 rare earth complexes include rare earth salts of five different anions have been synthesized and characterized.The research results show that all the complexes have bicapped structures of lanthanide-organic coordination cations.The structures of complexes can be affected remarkably by the counter anions.Based on crystal diffraction analysis,the influence of the counter anions to the complex structures, hydrogen bonds andπ-πstacking interactions in building novel supramolecular, and space topological structures in supermolecules have been studied.3.Four podand ligands L~Ⅲ-L~Ⅵcontaining different rigid framework and using [N-(phenylmethyl)]aeetamide as terminal groups and their 28 rare earth picrate complexes have been synthesized and characterized.The single-crystal X-ray analysis of the picrates complexes of L~Ⅲand L~Ⅳreveals that there are 1:1(M:L) type complexes with the rare earth ions coordinated with three bidentate picrate groups and four oxygen donor atoms from the tetradentate ligand.Based on crystal diffraction analysis,hydrogen bonds andπ-πstacking interactions in building novel supramolecular,and space topological structures in supermolecules have been studied.4.Three different podand ligands L~Ⅲ-L~Ⅵwith rigid framework using N-benzylsalicylamide and N-(3-pyridylmethyl)salicylamide as terminal groups and 31 rare earth nitrate and perchlorate complexes have been synthesized and characterized.The crystal structures of the complexes show that all the rare earth nitrate complexes of L~Ⅶand L~Ⅷare(6,3)honeycomb and(10,3)-a type coordination polymers,which are very uncommon in the rare earth complexes with podand ligands.5.Photoluminescence studies of europium and terbium complexes show that all the terminal groups have good sensitive function to europium and terbium ions. The framework and terminal groups of ligands,the counter anions have effects on the luminescent properties of rare earth complexes.6.The Eu/Tb complexes prepared in chapter two were intercalated into the interlayer space of MT by solid-liquid ion exchanging,and formed Eu/Tb-organic montmorillonite composite luminescent materials.The results of characterization show that the guest complex ions arranged in the interlayer space of MT in the formation of a monolayer and the composite materials formed through the supramolecular interactions between the host layers and the guest complex ions had regular layered structure.The luminescent properties of the composite materials were preliminarily studied.The result shows that the composite materials have better chemical and optical stabilities compared with their pure complexes.The ligands involved in the dissertation are listed as follows:L~Ⅰ:2,2’,2"-nitrilotris-(N-phenylmethyl)acetamideL~Ⅱ:2,2’,2"-nitrilotris-(N-phenyl)acetamideL~Ⅲ:2,2’-[(1,2-ethanediyl)bis(oxy)]bis[N-(phenylmethyl)]acetamideL~Ⅳ:2,2’-[(1,2-phenylene)bis(oxy)]bis[N-(phenylmethyl)]acetamideL~Ⅴ:2,2’-[(1,2-naphthalene)bis(oxy)]bis[N-(phenylmethyl)]acetamideL~Ⅵ:2,2’,2"-[(1,2,3-phenylene)tri(oxy)]bis[N-(phenylmethyl)]acetamideL~Ⅶ:2,5-bimethyl-1,4-bis {[(2’-benzylaminoformyl)phenoxyl]methyl} benzeneL~Ⅷ:1,3,5-tris{[(2’-benzylaminoformyl)phenoxyl]methyl} benzeneL~Ⅸ: 2,5-dimethyl-1,4-di{[2’-(3-pyridylmethylaminoformyl)phenoxyl]methyl}benzene更多还原