【作者】 张慧东；

【导师】 王悦；

【作者基本信息】 吉林大学 ， 有机化学， 2005， 博士

【摘要】 采用介孔分子筛MCM-41 或MCM-48 作为载体,与不同的发光传感分子组装得到不同用途的传感材料。通过对材料传感性能的考察可以发现,介孔分子筛的比表面积大、孔道排列规则有序、表面带有羟基、合成工艺简单、具有环境亲和力等众多特点使材料的性能得到极大的提高,验证了载体的不同可以改变传感材料性能的结论。合成了五种二亚胺钌配合物,与MCM-41 组装后得到具有氧气传感能力的材料。该材料的氧气透过率高,氧气分子与传感分子接触充分,且具有一定的独立性,可以直接应用于实际。其中[Ru(tmephen)3]2+/MCM-41 对氧气的灵敏度I0 /I100可以高达39.5,淬灭时间为1.7 s,还原时间为5.0 s。制备了两种金属卟啉铂化合物与MCM-41 的组装体,该组装体也具有高效的氧气传感能力。其中PtTMPyP4+/ MCM-41 性能更为优越:灵敏度为55.50,淬灭时间为0.33 s,还原时间为26.62 s。选择具有三维孔道结构的MCM-48 作为载体,得到了各项性能指标更好的氧气传感材料。以TTMAPP 为传感分子与MCM-41 形成组装材料,金属铜离子和锌离子会对该材料的发光光谱产生不同的影响,即使在金属离子浓度很低只有1 ppm 时,这种作用也是十分明显的,也就是说TTMAPP/MCM-41 对低浓度的金属离子也具有较高的灵敏度。设计、合成了一种长碳链喹吖啶酮衍生物BEDAHQA,利用MCM-41 作为载体与之组装得到传感材料。该材料具有金属依赖性,金属离子会使其发光淬灭。同时由于喹吖啶酮侧链上乙二胺基团的引入使发光基团与螯合基团分离,有效地避免了pH 值的影响。更多还原

【Abstract】 In recent years, the discoveries of sensing materials and devices have become extremely important in environmental and biological fields. A remarkable development of luminescent chemosensing materials has already been made because of their high sensitivity and selectivity. But the study is still localized on characteristics of compounds, it is a key for application that how to turn the compounds into materials and then to form devices. It is demonstrated that the direction in this field is to design and synthesize luminescent molecules and suitable matrix and then to assemble the molecules into the matrix to form materials or devices. So the development of new matrix is an important step for the sensing materials and devices. In this article we use mesoporous molecular sieves as a new class of matrix due to their high surface areas, ordered pore structure, narrow pore size distribution and hydroxyl-covered surfaces and select some organic or complex molecules with fine luminescent chemosensing properties. Then these functional molecules could be physically or chemically incorporated into mesoporous materials to obtain sensing materials, here mainly refer to oxygen sensing materials and metal ion sensing materials. Oxygen sensing material is usually composed of two parts, a support matrix and functional molecules of which the luminescent intensity is depended on the oxygen concentration. Oxygen molecule can quench the luminescence of the functional molecules through the pore of the matrix. Five diimine ruthenium complexes [Ru(bpy)3]2+, [Ru(dtBubpy)3]2+, [Ru(phen)3]2+, [Ru(dphphen)3]2+ and [Ru(tmephen)3]2+, have been synthesized and incorporated into MCM-41 to form sensing materials. The luminescent intensities of these materials decrease with increasing the oxygen concentration. The sensitivity I0/I100 (where I0 and I100 represent the detected luminescent intensities of the oxygen sensing materials exposed to 100% nitrogen and 100% oxygen, respectively.) satisfies the requirement of oxygen sensing materials, the quenching time is less than 2 s and the recovery time is less than 8 s. Especially of [Ru(tmephen)3]2+/MCM-41, the sensitivity is 39.5, the quenching time is less than 1.7 s and the recovery time is less than 5.0 s indicating the potential for the formation of oxygen sensing material or device. Compared with conventional oxygen sensing materials used polymers or silicones as matrix, the sensing properties used MCM-41 as matrix have been improved because MCM-41 can enhance the effective collision between the diimine ruthenium complexes and oxygen quencher. Therefore, oxygen sensing materials with higher performance are obtained. In order to study further the effect of mesoporous molecular sieves on the sensing materials, we have designed and synthesized two metalloporphyrins, PtTPyP and PtTMPyP4+, as sensing molecules and incorporated them into MCM-41 to fabricate materials with oxygen sensing properties. The performance of PtTMPyP4+/ MCM-41 is better than that of the other one, the sensitivity is 55.5, the quenching time is 0.33 s and the recovery time is 26.62 s. The same luminescent sensing molecule, PtTPyP, used MCM-48 as matrix instead of MCM-41 to form sensing material. Through the comparison between PtTPyP/MCM-41 and PtTPyP/MCM-48, it is shown that the sensitivity and respond time of the latter are higher than that of the former because the three-dimensional pore structure of MCM-48 benefit for the gas transition without barrier. The results indicated that controlling the structure of matrix would improve the performance of sensing materials. The research of metal ion sensing materials is focused on the field that the effect of luminescence of the sensing molecule with different metal ions. But for most metal ion sensing molecules, the poor hydrophlicity of the organic sensing molecules doesn’t benefit for the examination of the metal ions in water solution. We increased the hydrophlicity of the sensing materials by using MCM-41 as matrix with hydrophilic hydroxyl on the surface. And the metal ions in solution can be absorbed by MCM-41 for its pore structure that will enhance the sensitivity of the sensing materials for low concentration metal ion. The sensing material constituted of TTMAPP as luminescent molecule and MCM-41 as matrix. Emission spectrum study revealed that zinc (II) cation and copper (II) cation caused different luminescence changes of TTMAPP/MCM-41 even when the metal ion concentration was very low. It is much important for the development of metal ion sensing materials that the sensitivity is high for low concentration metal ions. We have also synthesized a quinacridone derivative with long alkyl chains, BEDAHQA, and used MCM-41 to improve the hydrophlicity of BEDAHQA/ MCM-41, which exhibits high luminescent property in solid state. Because of the ethylenediamine groups on the side chain of BEDAHQA, there is no direct interaction between the chelating group and the fluorophore, which avoids pH sensing. The luminescence of BEDAHQA/MCM-41 could be changed by the metal ions, especially when low concentration cobalt (II) cations existed, the更多还原