【作者】 王刚；

【导师】 金武松；

【作者基本信息】 东华大学 ， 有机化学， 2014， 硕士

【摘要】 在过去的十年里,石墨烯小分子因其在场效应晶体管,有机发光二极管以及光伏电池中的潜在应用引起科研工作者的极大兴趣,常见的石墨烯分子一般表现出p型半导体性质其空穴迁移率最高可达4.28cm2V-1s-1,但是在构建p-n异质结结构和互补的逻辑电路中,n型半导体是必不可少的,然而现阶段n型有机半导体还是很匮乏,所以制备高性能的n型有机半导体是材料研究的焦点。Houk等提出的一种制备n型有机半导体策略是用氮原子取代石墨烯中的碳原子,由于N原子高的电负性,该类分子具有出色的电子传输能力。本论文主要分为三部分：一、氮杂分子石墨烯的合成与表征。以5-溴-2-碘嘧啶等为起始原料,合成了5种具有不同氮原子数及结构的分子石墨烯前躯体8,20,21,41和51。通过对这些前驱体关环条件系统的探讨发现,前驱体8,21和41在所选择的氧化关环条件下不发生关环反应；而前驱体20在利用MALDI-TOF mass进行追踪反应时发现有关环产物生成,但是由于产物稳定性差的原因,我们没有能够分离出产物；前驱体51可以通过Scholl氧化脱氢关环反应制备了氮杂分子石墨烯TM3b。通过NMR、MADLI-TOF mass、UV、FL等手段对合成的氮杂分子石墨等烯TM3b进行表征。二、配合物的合成与表征。我们对化合物8,20和21在常温下与银盐配位进行了探讨。我们利用NMR、UV、FL对所得到配合物进行了表征。从表征结果上看嘧啶环上的氮原子很容易与银离子发生配位并影响化合物的空间结构和光学特征。三、有机金属框架材料的合成与表征。我们用化合物41作为配体去制备金属有机框架材料。我们利用TG、SEM、TEM、ESEM、 XRD对所合成的金属有机框架材料进行了一些基本的物性测试。结果显示该材料不仅具有规则的外部形貌,同时内部结构具有晶体学特征。更多还原

【Abstract】 In past decades, there has been significant interest in developing small graphene molecules of their potential applications in semiconducting devices such as organic field effect transistors, organic light-emitting diodes, and photovoltaic cells. The graphene molecules commonly display p-type characteristics and the hole mobility of thin films can go as high as4.28cm2V-1s-1, However, n-type organic materials, which are the required in semiconducting devices to complete p-n junctions or complementary logic behaviors are obviously lacking. Currently, pursuing high-performance n-type materials has become the focus of materials research. One strategy suggested by Houk et al. is that to replace carbon atoms in grapheme by nitrogen atoms.N-doped Graphene molecules could exhibit promising electron-transport behaviors because of their high electron affinities.The main work includes three parts:Part I:Synthesis and characterization of nitrogen-doped molecule graphene. The molecule graphene precursors8,20,21,41and51with different nitrogen atom number and structure were successfully synthesized from5-bromo-2-iodo pyrimidine by several steps. The experimental results showed that8,21,41could not be cyclized under the chosen oxidizing conditions. Although oxidative cyclized product from precursors20was found by MALDI-TOF mass, the final product was not obtained due to the poor stability. TM3b was successfully synthesized by oxidative cyclization of the corresponding precursor51, and TM3b was characterized by NMR、 MALDI-TOF mass、UV、FL.Part II:Synthesis and characterization of coordinated compound. The coordination of the hexaarylbenzene8,20and21with silver salt was discussed. The results of UV、FL and NMR measurements showed that the nitrogen atom on pyrimidine ring easily coordinated with silver ion and then affected the spatial structure and optical properties. PartⅢ:Synthesis and characterization of metal-organic framework materials. The41was used as ligand to synthesis metal-organic framework materials (MOF). The results of TG、XRD、 SEM、ESEM and TEM exhibited not only ordered external morphology, but also internal crystallography characteristics.更多还原