【作者】 吴敏；

【导师】 金武松；

【作者基本信息】 东华大学 ， 有机化学， 2013， 硕士

【摘要】 共价有机框架(Covalent organic framework,COF)材料由于具有多孔及大表面积,在能量贮藏、催化、分离、光学器件和化学传感等方面具有潜在的应用前景,因此对COF材料的开发及应用的研究已经成为一个新兴的研究领域。与通过氢键或配位键形成的氢键缔合骨架、金属有机框架材料相比,直接通过共价键连接形成的COF材料,骨架结构更稳定,具有优异的耐热性和耐水解性。COF材料的性能与刚性骨架单元的设计选择直接相关,目前对刚性骨架的选择主要集中在卟啉、酞菁、苯并菲、芘等少数化合物上,从而极大的限制了COF材料性能的开发。菲啰啉作为一类重要的含氮原子的有机共轭分子,不仅具有极高的稳定性,而且还具有优良的光电活性及配位等性质。因此,以菲啰啉为基本骨架的COF体系,有可能显示与以往不同的新的性质。本论文主要包括以下内容：(1)卤代菲啰啉单体衍生物的合成。为合成环状三聚体,我们选择了2,9-位上含有卤素的菲啰啉作为前驱体。首先我们尝试了合成反应性能较好的溴取代化合物7,希望以它为前驱体合成刚性骨架10。但在实验过程中发现由于极性等原因无法分离提纯化合物7,因此改用反应性稍差的氯取代菲啰啉9为聚合单体,并成功的分离得到了纯净的化合物9。(2)组成COF刚性单元的环状菲啰啉三聚体的合成。首先利用氯取代化合物9与双频哪醇硼酸酯为起始原料,探讨了在Pd催化下,通过Suzuki-Miyaura偶联反应合成刚性骨架10。通过对反应温度及溶剂的探讨,分别得到线性菲啰啉二聚体11和脱掉氯原子的副产物12。通过Ni催化的Ullmann反应(乌尔曼反应),以化合物9为起始原料成功的合成出环状菲啰啉三聚体10,并经MALDI-TOF-Mass测试验证了其结构。另外为了考察环状菲啰啉三聚体的溶解性,我们尝试合成了含有十二烷基长链的环状菲啰啉三聚体化合物14。通过Ullmann反应(乌尔曼反应)成功的合成出了溶解性较好的刚性骨架14,但是由于受到分离方法的局限,化合物14没有能分离提纯。(3)含有环状菲啰啉骨架的COF体系的探讨。最后利用环状菲啰啉三聚体10为刚性骨架,对构筑新型COF体系进行了初步探讨。更多还原

【Abstract】 Because the potential applications in the fields of energy storage, catalysis, separation, optical device and chemical sensing, the study on the covalent organic framework (COF) materials with their porosity and large surface area have become a new research field. Compared with the materials consisted of hydrogen bond associated skeletons or metal organic frameworks from coordination bonds, directly covalently bonded COF materials are more structurally stable with excellent heat resistance and hydrolysis resistance.The properties of COF materials are directly related to the design of the rigid skeleton unit. To date, the rigid frames mainly focus on a few compounds, such as porphyrin, phthalocyanine, triphenylene and pyrene etc., which greatly limits the development of COF materials. As an important class of nitrogen-containing organic conjugated molecules, phenanthroline possesses not only high stability but also excellent photoelectric activity and coordination feature and so on. Therefore, COF materials with phenanthroline as basic skeleton are expected to display new properties.This thesis mainly includes the following contents:(1) The synthesis of the monomer derivatives of halogen substituted phenanthroline.To synthesze the cyclic trimer,2,9-halogenated phenanthroline was chose as precursor. At first, the bromo-substitued compound7with high reactivty was prepared, which was proposed to be the precursor to syhthesize the rigid skeleton10. However, due to the polarity, it was difficult to separete out.Then chloro-substitued compound9with less reactivity was selected as the monomer, and the pure compound9was successfully obtained.(2) The synthesis of cyclic phenanthroline trimer of COF rigid unit.At first, with chloro-substitued compound9and bis(pinacolato)diboron as starting materials, rigid skeleton10was prepared through Suzuki-Miyaura coupling reaction with Pd-catalyst. By adjusting the reaction temperature and solvent, linear diphenanthroline11and dechlorinated by-product12were obtained respectively. Using compound9as starting materials through Ullmann reaction with Ni-catalyst, cyclic phenanthroline trimer10was successfully synthesized, which was verified by MALDI-TOF-Mass. On the other hand, to study the solubility of cyclic phenanthroline trimer, compound14with dodecyl chain was synthesized through Ullmann reaction. Although rigid skeleton14showed better solubility, no pure one was obtained due to the limitation of separation methods.(3) Application of cyclic phenanthroline frame for COF materials.With cyclic phenanthroline trimer10as rigid skeleton, the preliminary study to construct COF system was discussed.更多还原