【作者】 包志红；

【导师】 任咏华； 吴立新；

【作者基本信息】 吉林大学 ， 物理化学， 2008， 博士

【摘要】 光致变色是一种化学物理现象,包含有机、无机、生物、高分子等领域的光诱导化学和物理反应。有机光致变色化学与材料的研究近年来得到了不断拓展与深入,由于螺嗪化合物具有较高的光稳定性和抗疲劳性,成为研究的热点。然而,这个体系的研究被限制在纯的有机体系,带有金属配合物的研究很少。研究光致变色部分引入到含金属框架结构中能够为设计和合成新的具有优异性质的光致变色材料提供新的可行的方法。首先我们设计和合成了含有螺嗪光致变色的配体(L1)以及它的带有硫醇的金属锌配合物(1a-1e),研究了这些配合物溶液的光物理及其光致变色性质。其次我们又合成了带有长烷基链的螺嗪配体(L2)及它的硫醇锌配合物(2a),希望可以在LB膜材料上研究此种物质的光致变色性质。接着我们又将发光性质很好的金属铼与配体L1结合,然后通过一个带有长烷基链的单吡啶与铼配位,从而得到一个能够形成很好LB膜的光致变色物质(Re-1, Re-2),最终得到了一个即具有光致变色性质又可以光致发光的膜材料。多金属氧簇又称多酸是早期过渡金属元素,它具有丰富的结构和众多的组成成分,这使其展示出许多有趣的性质,但从材料的角度来讲它是一种不易加工的材料。利用带有电荷的阳离子表面活性剂代替多酸表面的抗衡离子能够形成含多酸的有机/无机复合物,它具有良好的可加工性和自组装特性。但通常采用的阳离子表面活性剂一般都为简单的纯有机物质,而采用金属有机配合物作为表面活性剂的研究比较少,在本论文里我们将带有电荷的铼联吡啶配合物作为表面活性剂,采用静电包埋的方法与不同电荷数和不同形状的多酸静电复合,得到了一系列新颖的带有金属配合物的多酸复合物,通过对复合物光谱的研究,初步发现不同类型的多酸对铼金属配合物的发光性质的影响有明显不同。更多还原

【Abstract】 Photochromism is a chemistry and physical phenomenon and involves photo-chemistry and physical reaction that are relevant to the field of organic chemistry, inorganic chemistry, biochemistry and macromolecular science. In the development and investigation of organic photochromism and its material properties, spirooxazine is one of the well-known families of photochromic molecules which provide good photo-stability and high fatigue resistance properties and was studied widely. However, the studies of all these systems are confined to pure organic systems with very few precedents in the incorporation of such moieties into the metal-containing inorganic or organometallic counterparts. It is envisaged that incorporation of the photochromic moieties into the metal-containing framework would provide a new and alternative approach towards the design and synthesis of new photochromic materials with perturbed properties.Firstly, a spirooxazine-containing 2,2’-bipyridine ligand （L1） and a series of its zinc（II） thiolate complexes （1a–1e） have been designed and successfully synthesized. Their photophysical and photochromic properties in solution were studied. Upon excitation by UV light, all the ligands and complexes exhibit photochromic behavior. On conversion to the open photomerocyanine （PMC） form by UV excitation, the ligands and all zinc complexes display luminescence at ca. 720 nm in EtOH–MeOH （4:1 v/v） glass at 77 K. The thermal bleaching kinetics of the ligands and the complexes were studied in DMF at various temperatures. A linear relationship between the activation enthalpy and entropy was seen and an isokinetic temperature of 295.4±1.5 K was estimated. The photochemical quantum yields for the photochromic reactions of the ligands and complexes were also determined.In addition, a long hydrocarbon chain-containing spirooxazine （L2） and its zinc（II） bis-thiolate complex （2a） were synthesized for preparation of LB film. Photochromic properties of the LB film were also studied. Luminescent spirooxazine-containing Re（I） complexes with long hydrocarbon chains （Re-1, Re-2） were synthesized, and their photophysical and photochromic properties in solution and film （LB film and cast film） were studied. Both the UV-visible absorption and luminescence intensity of the LB films and cast films were found to be changed with ultraviolet light （365 nm） and visible light （610 nm） irradiation.Polyoxometalates （POMs） are the polyoxoanion of the early transition elements, especially vanadium, molybdenum and tungsten. They are discrete and uniform cluster anions that assembled from small metal oxysalt fragments in water solution with a certain pH value. The variety of their composition and structures endowed them with many functional properties, such as catalysis, proton conductivity, nonlinear optics, medicine, photophysics and magnetism. However, the development of materials and devices based on POMs was restricted because of their higher lattice energies, lower stability and poor processibility. In is necessary that new methods should be explored to combine, position and orient the clusters, indicative of the physical and chemical properties of the POMs. Organic/inorganic complex can be formed by using cationic surfactants to replace the counterions covered on the surface of POMs, it can be regarded as a novel supra-molecular soft material. Recent reports suggested that the different functions of the assembly are a direct result of the structure formed. However, the cationic surfactants employed are usually pure organic systems and cationic surfactants containing metal centers were rarely used. In chapter 4, rhenium （I） bipyridine surfactants with positively charged groups (RebpyNC₁₈) were designed and synthesized. It showed strong 3MLCT [Re（dπ）→π*（diimine）] luminescence. Different polyoxometalates [H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀, Na₉EuW₁₀O₃₆, K₁₃Eu(SiW₁₁O₃₆)₂] were encapsulated with RebpyNC18 surfactant and the photophysical properties of the these SECs were studied. Different polyoxometalates were shown to change the luminescence properties of the Re（I）-bipyridine complexes.In summary, photochromic spirooxazine-containing ligands and their zinc（II） and rhenium（I） complexes were designed, synthesized and their photochromic properties in solution and films were studied. Surfactants containing rhenium（I） have been used to encapsulate different types of POMs and their luminescence properties have been found to be influenced by the nature of the POMs.更多还原