双核咪唑啉类NCN型钳形铂化合物的合成与性质

发布时间：2017-12-27 01:13

本文关键词：双核咪唑啉类NCN型钳形铂化合物的合成与性质　出处：《郑州大学》2016年硕士论文　论文类型：学位论文

【摘要】：在过去几十年里有机铂化合物由于其丰富的光学性质而得到了大量的研究,研究表明它们吸收和发射的能量容易通过利用辅助配体的电子性质进行调节。平面四配位的有机铂化合物在光学传感器,光催化作用,荧光探针,气致变色,离子识别和分子光化学太阳能能量转化设备等广泛领域内存在潜在的应用价值,有机铂化合物也被成功应用于磷光发射的有机发光二极管(OLED)设备中,因而引起了人们广泛的关注与兴趣。在本文中,主要通过刚性的聚对亚苯基结构桥联咪唑啉类钳形金属铂化合物合成了三种双核钳形金属铂化合物(Scheme 1),并对该类化合物在室温下二氯甲烷溶液中的电子吸收和发射性质进行了研究。在紫外可见吸收光谱中,所有的化合物在波长210-250 nm处有强的吸收峰,在300-380 nm处有中等强度的吸收峰,这些吸收峰被认为是配体内部的π-π*的电子跃迁引起的,在400-450 nm处有弱的吸收峰,这些低能量的吸收被暂定为MLCT(金属到配体的电子转移)电子跃迁引起的。这些化合物在二氯甲烷溶液中的最大发射波长为594-595 nm,被归为3MLCT过程,通过对不同浓度的发射波谱测定,表明所有的化合物在二氯甲烷溶液中不存在聚合的作用。用1M H2SO4的硫酸奎宁溶液(Ф=0.546)作为参比测得化合物在脱气的二氯甲烷中的量子效率为0.84%-1.3%。使用密度泛函(DFT)的计算方法对双核钳形铂化合物的结构和前线轨道进行了理论计算的研究。
[Abstract]:In the past few decades, organic platinum compounds have been extensively studied due to their rich optical properties. Studies show that the energy of their absorption and emission is easily regulated by the electronic properties of the auxiliary ligands. The plane four coordinated organic platinum compounds in optical sensors, photocatalysis, fluorescent probe, Gaschromic, has potential application fields of ion recognition and molecular photochemical energy conversion equipment such as solar energy, organic platinum compounds have been successfully applied in phosphorescent organic light emitting diode (OLED) emission device, which caused the the attention and interest. In this paper, mainly through the rigid polymer synthesized three binuclear platinum compounds on the metal clamp clamp metal platinum compound phenylene bridged structure of imidazoline (Scheme 1), and the compounds in dichloromethane solution at room temperature electronic absorption and emission properties were studied. In the UV Vis absorption spectra of all compounds have strong absorption peak at the wavelength of 210-250 nm, a medium intensity absorption peak in 300-380 nm, the absorption peak is believed to be caused by internal ligand pi pi * electronic transition, there are weak absorption peaks at 400-450 nm, the low energy absorption is tentatively scheduled for MLCT (electron transfer metal to ligand) by electron transition. The maximum emission wavelength of these compounds in dichloromethane solution is 594-595 nm, which is classified as 3MLCT process. The emission spectra of different concentrations indicate that all compounds do not exist in dichloromethane solution. Using quinine sulfate solution 1M H2SO4 (with =0.546) as reference compounds measured quantum efficiency in the degassing in dichloromethane was 0.84%-1.3%. Using density functional theory (DFT) structure and frontier orbital of binuclear pincer platinum complexes were studied the calculation methods of the theoretical calculation.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O627

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