摘要
环金属化铱配合物具有发光效率高、发光颜色可以通过改变配体结构进行调节及磷光寿命较短等优点而成为研究的热点。而详细研究配体化学结构与配合物发光性能的关系(即构效关系)的研究和阐明配合物的发光机理是设计新型、高效发光材料的理论基础和关键因素。
本论文设计并合成了一系列新型以2-苯基喹啉为主配体、酰胺化合物为辅助配体的新型环金属化铱配合物的有机发光材料。先对氯桥二聚铱配合物(pq)_2Ir(μ-Cl)_2Ir(pq)_2(其中pq=2-phenylquinoline)中Ir-Cl键的稳定程度进行研究,合成得到了吡啶的铱配合物(pq)_2Ir(pyridine)Cl。具体的合成方案为:将吡啶与氯桥二聚铱配合物(pq)_2Ir(μ-Cl)_2Ir(pq)_2在二氯甲烷溶液中回流生成目标的配合物(pq)_2Ir(pyridine)Cl。然后合成了酰胺的铱配合物,具体的合成方案为:将酰胺化合物与氯桥二聚铱配合物(pq)_2Ir(μ-Cl)_2Ir(pq)_2在高温、弱碱存在的条件下反应生成目标的化合物——(pq)_2Ir(acetylaniline),(pq)_2Ir(N-tert-butylbenzamide),(pq)_2Ir(N-phenylbenzamide)及(pq)_2Ir(pyridine)。对所得到的产物进行了红外、核磁、单晶衍射及元素分析表征,确定了所得配合物为目标产物。
并对得到的配合物进行了紫外和荧光的光学性质研究。此类化合物都具有相类似的紫外和荧光光谱,但由于结构不同,紫外吸收波长和荧光发射波长都存在不同程度的位移。荧光光谱表明,此类配合物在590nm左右有强的荧光发射,表明这些化合物是良好的红光发光材料。同时对这些配合物通过循环伏安法测定了电化学性质,并以此确定了其HOMO和LOMO能级。此类配合物有较好的氧化-还原可逆性,其良好的发光性能及稳定性使此类材料具有很好的应用前景。
Recently, iridium complex have received considerable attention because of their high emission efficiencies and easy tuning of emission colors by changing chemical structures of ligands.An efficacious solution to this problem is to modify the structrure of ligands or introduce phosphorescent dye into the polymer chain by grafting.
In this thesis a series of heteroleptic cyclometalate Ir complexes with acylamide derivants as ancillary ligands (pq)_2Ir(LX) (pq=2-phenylquinoline,LX=acetylaniline, N-phenylbenzamide,N-tert-butylbenzamide,pyridine) have been successfully synthesized. At first, the iridium complexe containing pyridine ligands was synthesized in order to confirm the stabilization of Ir-Cl bond. The synthetic procedures are as follows: (pq)_2Ir(μ-Cl)_2Ir(pq)_2 was refleuxed with pyridine, and obtained the (pq)_2Ir(pyridine)Cl. Then the Ir complexes containing amides ligands were synthesized. The synthetic procedures are as follows:Stirred the dicholoro-phenylquinoline complex and amide derivants in the presence of alkali in 2-ethoxyethanol to give birth to the aimed complexes,these are (pq)_2Ir(acetylaniline), (pq)_2Ir(pyridine),(pq)_2Ir(N-Phenylbenzamide),(pq)_2Ir(N-tert-butylbenzamide).All of the structures of complexes were characterized by HNMR, x-ray single crystal diffusion or element analysis.
All the complexes give rise to resemble absorptions at around 260nm, and their solution emissions are all fell into the red light region but differ in the max emission wavelength around 590nm, which prove all the complexes are red phosphorescence complexes. The cyclic voltammetry spectra of these complex show that they are redox reversibility The stability of devices can be expected due to their excellent redox stabilities.
引文
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