中性Cu(I)配合物的合成及光电性能研究

项目名称： 中性Cu(I)配合物的合成及光电性能研究

项目编号： No.20874098

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 轻工业、手工业

项目作者： 程延祥

作者单位： 中国科学院长春应用化学研究所

项目金额： 35万元

中文摘要： 本项目首先利用既可以形成离子型又可以制备中性铜(I)配合物的配体合成了一系列成对的离子型和中性铜(I)配合物，每一对配合物拥有完全相同的骨架结构但有差异的光物理性质。相对于离子型铜(I)配合物，中性配合物发射蓝移，具有更高的光致和电致发光效率和更长的发射寿命，这些研究结果表明了中性铜(I)配合物拥有与离子型铜(I)配合物相近的发光性能，是一类有效的电致发光材料。另一方面的工作是利用不同共轭程度的芳香类配体，设计合成了几类"纯"中性铜(I)配合物。其中，吲哚衍生物铜(I)配合物展示了分别来自MLCT和ILCT的双峰发射。这类配合物可以作为比率传感器用于检测氧气，最大响应比值为3.2，不同于经典铜(I)配合物，这类配合物的传感机理是由能量转移和电子转移协同实现的。随着共轭程度增加，配合物中ILCT跃迁能隙降低，而配体与金属之间的作用减弱，不能发生有效的自旋-轨道耦合作用，进而无法进行自旋禁阻的MLCT跃迁，因此部分配合物仅表现荧光发射，这些结果说明了配体的优选是过渡金属配合物设计合成的一个主要因素。此外，本项目还设计合成了可溶液加工的树枝状铜(I)配合物及其他过渡金属发光配合物。

中文关键词： 中性铜(I)配合物；合成；磷光；荧光；电致发光

英文摘要： In this project, a series of the paired ionic and neutral heteroleptic Cu(I) diphosphine complexes have been synthesized firstly using these ligands that can not only form the cationic Cu(I) complexes, but also prepare neutral complexes by removing the active H atom in the presence of strong base. These complexes possess completely identical skeletons but quite different photophysical properties in each pairs. The neutral complexes show blue-shifted emission, much higher quantum efficiencies and longer lifetimes relative to the corresponding ionic ones. They also exhibit a higher current efficiency. The results obtained from the study of PL and EL have demonstrated that the neutral CuI complexes possess similar luminescent performance to ionic ones and are a kind of more effective phosphorescent emitter for OLEDs. Second, kinds of "pure" neutral Cu(I) complexes have been prepared using the aromatic ligands with different conjugation. The complexes containing indolyl derivatives show unusual dual-emission originated from the ILCT and MLCT transitions when they were dispersed in rigid matrix. The film containing 10 wt% of one of these complexes in PMMA exhibits the ratiometric fluorescent oxygen gas sensing property with the response ratio 0.3 to 3.2. The sensing mechanism of these neutral molecules is attributed to the synergetic effect of the energy and charge transfer. Parts of complexes only have singlet fluorescence instead of the expected phosphorescence. A reasonable explanation is that the increased conjugation in the ligands after deprotonation decreases the energy level of πrbital, which inhibits the effective spin-orbital coupling. These results imply that the careful selection and rational design of the ligands maintaining a matched energy level with metal d orbitals are the key factors to take full advantage of the triplet excited states in organic-metal complexes. Moreover, the Cu(I) dendrimers have also been reported in this project.

英文关键词： Neutral Cu(I) complexes; synthesis; phosphorescence; fluorescence; electroluminescence