【作者】 王海平；

【导师】 唐瑜； 唐宁；

【作者基本信息】 兰州大学 ， 无机化学， 2010， 博士

【摘要】 被誉为新材料宝库的稀土元素因其特殊的电子层结构和成键特征,使得稀土化合物表现出独特的化学及物理性质,在光、电、磁等领域得到广泛应用。稀土元素以其发射谱带窄、色纯度高、荧光寿命长、量子产率高,以及温度、浓度淬灭小等特点,在发光材料中独树一帜。稀上发光配合物不但具有无机物稳定性好的优点,而且拥有有机物量子产率高的特点,还可以进一步通过分子设计及分子自组装实现结构的调控及性能的复合,备受科研工作者的关注。在课题组已有工作基础上,以2-甲基-8-羟基喹啉为原料,设计合成了-系列喹啉-酰胺型配体及其稀土配合物,在结构表征的基础上,对铕配合物的荧光性质进行了研究,并以荧光信号为表达,在溶液中测定了铕配合物对阴离子的选择性识别；同时以介孔材料MCM-41和SBA-15为基质,以其孔道为“微反应器”,成功的将此类配体以共价键的形式接枝于基质孔道中,制备出相应的稀土配合物杂化材料,X-射线粉末衍射、N2吸附和透射电镜均表明,配合物分子的引入并未破坏介孔材料自身的结构,在此基础上我们探讨了基质对配合物分子光物理性质的影响。本论文共分为四部分：第一章：简要概述了稀土发光配合物及其有机-无机杂化发光材料的研究进展；第二章：以2-甲基-8-羟基喹啉为骨架,设计、合成出两类共十二种配体(L1-12),并进一步合成了其稀土硝酸盐、苦味酸盐共24个系列144个配合物。通过元素分析、摩尔电导、红外光谱和X-射线单晶结构分析等手段对配合物的组成和结构进行了表征。研究结果表明,配体均以类环状配位构型与中心金属离子螯合配位,阴离子对配合物的结构没有明显影响。第三章：对L1-12的铕配合物进行了荧光性质研究,结果表明,该类型配体对铕离子具有良好的敏化作用；同时考察了配体末端基、抗衡阴离子以及溶液中溶剂分子对中心铕离子发光行为的影响；考虑到配体配位点不饱和,配合物中铕离子易受抗衡阴离子影响的特点,研究了在溶液中该类型配体铕配合物对阴离子的荧光响应识别实验。第四章：以介孔材料MCM-41和SBA-15为基质,将设计、合成的含醛基的喹啉-酰胺型前驱化合物以形成Schiff碱键的形式共价接枝于MCM-41和SBA-15介孔材料的孔道中,并进一步与稀土离子反应,组装出新型介孔稀土配合物杂化材料。用元素分析、红外光谱、X-射线粉末衍射、氮气(N2)吸附和电镜扫描等手段对杂化材料的组装和微结构进行了表征；在此基础上,对杂化材料的荧光光谱、量子产率、荧光寿命和光稳定性等进行了研究,并探讨了基质微环境与配合物分子之间的相互作用对稀土离子发光行为的影响。本论文涉及的配体如下：L1：8-(2-(1’,3’-二氧代-2’-环戊基)喹啉)-氧代-N-苯基乙酰胺L2：8-(2-(1’,3’-二氧代-2’-环戊基)喹啉)-氧代-N-苄基乙酰胺L3：8-(2-(1’,3’-二氧代-2’-环戊基)喹啉)-氧代-N,N-二苯基乙酰胺L4：8-(2-(1’,3’-二氧代-2’-环戊基)喹啉)-氧代-N,N-二异丙基乙酰胺L5：8-(2-(1’,3’-二氧代-2’-环戊基)喹啉)-氧代-N-乙酰六氢吡啶L6：8-(2-(1’,3’-二氧代-2’-环戊基)喹啉)-氧代-N-乙酰吗啉L7：8-(2-(1’,3’-二氧代-4’甲基-2’-环戊基)喹啉)-氧代-N-苯基乙酰胺L8：8-(2-(1’,3’-二氧代-4’甲基-2’-环戊基)喹啉)-氧代-N-苄基乙酰胺L9：8-(2-(1’,3’-二氧代-4’甲基-2’-环戊基)喹啉)-氧代-N,N-二苯基乙酰胺L1O：8-(2-(1’,3’-二氧代-4’甲基-2’-环戊基)喹啉)-氧代-N-二异丙基乙酰胺L11：8-(2-(1’,3’-二氧代-4’甲基-2’-环戊基)喹啉)-氧代-N-乙酰六氢吡啶L12：8-(2-(1’,3’-二氧代-4’甲基-2’-环戊基)喹啉)-氧代-N-乙酰吗啉更多还原

【Abstract】 The shielding of the 4f electrons from interactions with their surroundings by the filled 5s2 and 5p6 orbitals is responsible for the interesting chemical and physical properties of the rare earth elements which be known as the treasure house of new materials. A lot of the luminescentrare earth compounds have been applied in light-conversion molecular devices and inorganic or organic light-emitting devices, because the outstanding optical properties of the rare earth cations such as long-lived, line-shaped, and position-defined luminescence. Recently, the design and assembly of functional luminescent rare earth complexes have become a challenging issue, because the organic ligand-sensitized complexes combine the outstanding optical properties of the central cations and the regulated structures of complexes with designed organic ligands. The quinoline-amide type ligands which derived from 2-substituted-8-hydroxyquinoline as the central skeleton and their rare earth complexes have been designed and synthesized. Based on the characterizations of the complexes, solid-state and solution luminescent properties of the complexes were researched. Considering the coordinatively unsaturated characters of ligands, europium complexes with the quinoline-amide type ligands might exhibit anion-responsive luminescence profiles for particular anions. The anion-selective experiments of the europium complexes with the quinoline-amide type ligands were accomplished subsequently. Meanwhile, the quinoline-amide type ligands have been immobilized in the mesoporous matrices (MCM-41 or SBA-15) and the structures of the mesoporous matrices have been determined that the highly ordered mesoporous structures were retained after the complexes covalently bonded to the channels of the matrices by the powder X-ray diffraction (PXRD), transmission electron microscope (TEM), and nitrogen (N2) adsorption/desorption. The luminescence behaviors of the complexes bonded in the mesoporous matrices were investigated and the structure-property relationships of the mesoporous hybrid materials were studied.The dissertation includes following five chapters:Chapter 1:A brief review of investigation progress of rare earth luminescent complexes and their luminescent hybrid materials were summarized.Chapter 2:Quinoline-amide type ligands L1-12 have been designed and synthesized from 2-substituted-8-hydroxyquinoline as the central skeleton and 144 rare earth complexes include rare earth nitrate and picrate with L1-12 have been synthesized and characterized. The composition and structure of the complexes can be characterized by means of elementary analysis, molar conductance, IR and single-crystal X-ray analysis. The results determined that the ligands wrap around the metal ion with its coordination groups and the structure of the complexes were not influenced obviously by the anion.Chapter 3:Photoluminescence studies of europium complexes show that the quinoline skeletons have good sensitive function to europium ions. The results of the triplet state energy levels T1 of the ligands L1-12 indicated that these ligands are suitable sensitizers for europium. Considering the coordinatively unsaturated characters of the quinoline-amide type ligands, europium complexes with ligands L1-12 might exhibit anion-responsive luminescence profiles for particular anions, because the stoichiomatry, geometry, and structure of the ternary "ligand-lanthanide-anion" complex are often alerted by the additional coordination from external anion. The Eu3+ complexes with ligands L1-12 exhibited the similar anion-response luminescence behaviors which the luminescence increased upon addition of both Cl- and NO3-.Chapter 4:Novel organic-inorganic luminescent mesoporous hybrid materials were assembled through the coordination reaction between europium nitrate with chelated quinoline-amide type ligands immobilized in the mesoporous materials (MCM-41 and SBA-15). The mesoporous hybrid materials were characterized by elemental analysis, Fourier transform infrared spectra, powder X-ray diffraction (PXRD), transmission electron microscope (TEM), and nitrogen (N2) adsorption/desorption. The results demonstrated that the highly ordered mesoporous structures were retained after the complexes covalently bonded to the channels of the matrices. The SBA-15-type hybrid materials, which pore size is twice of MCM-41, display more efficient emission due to the spatial confinement of the nanochannel of mesoporous matrix. This deduction may be validated deeply by the fact that the influences are more obvious for the complexes including rigid end group ligands. In addition, the Eu3+ complexes coordinated with the ligands containing rigid end groups in MCM-41 matrices exhibit better photoluminescence stability upon exposure to ultraviolet light.The ligands involved in the dissertation are listed as follow: L1:2-(2-(1,3-dioxolan-2-yl)quinolin-8-yloxy)-N-phenylacetamide L2:2-(2-(1,3-dioxolan-2-yl)quinolin-8-yloxy)-N-benzylacetamide L3:2-(2-(1,3-dioxolan-2-yl)quinolin-8-yloxy)-N,N-diphenylacetamide L4:2-(2-(1,3-dioxolan-2-yl)quinolin-8-yloxy)-N,N-diisopropylacetamide L5:2-(2-(1,3-dioxolan-2-yl)quinolin-8-yloxy)-1-(piperidin-1-yl)ethanone L6:2-(2-(1,3-dioxolan-2-yl)quinolin-8-yloxy)-1-morpholinoethanone L7:2-(2-(4-methyl-1,3-dioxolan-2-yl)quinolin-8-yloxy)-N-phenylacetamide L8:2-(2-(4-methyl-1,3-dioxolan-2-yl)quinolin-8-yloxy)-N-benzylacetamide L9:2-(2-(4-methyl-1,3-dioxolan-2-yl)quinolin-8-yloxy)-N,N-diphenylacetamide L10:2-(2-(4-methyl-1,3-dioxolan-2-yl)quinolin-8-yloxy)-N,N-diisopropylacetamide L11:2-(2-(4-methyl-1,3-dioxolan-2-yl)quinolin-8-yloxy)-1-(piperidin-1-yl)ethanone L12:2-(2-(4-methyl-1,3-dioxolan-2-yl)quinolin-8-yloxy)-1-morpholinoethanone更多还原