手性稀土配合物/高分子杂化材料的合成及圆偏振荧光性质研究

Chiral lanthanide complexes is a kind of special materials that extensively used for circularly polarized luminescence (CPL) research. As promising CPL materials, it must meet all the requirement of the high luminescent yield, high CPL activity and easy device fabrication. Unfortunately, the lanthanide complexes, which have poor solubility, thermodynamic stability and poor volatility, completely unmask the disadvantage of their difficultily machining process from material to device fabrication. Inorganic-Organic hybrid Materials will not only essentiallysolve this disadvantage, but also keep the CPL performance of the complexes. In this project, we would like to employ chiral monomer with lanthanide coordination moities to synthsize the chiral polymer, then complex these polymer with chiral lanthanide complexes to fabricate a series of chiral lanthanide complexes hybrid polymers. According to rational tailor for the chiral monomer, the polymer will possess the ability of sensitizing the lanthanide luminescence, meanwhile the ability of chiral transfer from polymer to the metal centers. The project will mainly investigate the synthesis of the chiral lanthanide polymer, energy level match between the excited states of the polymer and lanthanides, and the potential factors of the chiral synergistic effect between the polymer backbone and the chiral ligands. If the project is accomplished, should the high CPL activity of the lanthanide complexes and the easy device fabrication will be expect ar the same time, and will take a big leap for the materials forward to practical application.

手性稀土配合物是一类广泛用于圆偏振荧光(CPL)研究的特殊发光材料。作为理想的CPL材料，材料本身必须同时兼具发光效率、圆偏振度和易机械加工性。但稀土配合物由于其在溶剂中较差的溶解性、热稳定性及低挥发性，使其在由材料向器件的转化过程中难加工的缺点暴露无遗。无机-有机高分子杂化材料在保持材料CPL性能的基础上可以从本质上解决材料难加工的缺点。本项目拟采用具有稀土配位能力的手性单体作为手性源合成手性高分子聚合物，然后与手性稀土配合物进行复合构筑一系列手性稀土高分子杂化材料。通过对手性单体的修饰使高分子聚合物兼具敏化稀土离子能力和手性传递能力。本项目将围绕手性稀土高分子的合成，高分子激发态能级与稀土离子的能级匹配，高分子主链的手性与配体手性协同效应对圆偏振光的影响等因素展开研究。该项研究如能达到目标，将在提高手性稀土配合物CPL活性同时显著改善材料加工性能，使CPL材料向实用化迈进一大步。

为解决具有圆偏振发光性质的手性稀土配合物在由材料向器件转化过程中因难加工而无法得以应用的关键问题，我们提出了通过无机-有机高分子杂化的方式从本质上解决材料难加工的缺点。本项目针对手性稀土配合物及其高分子杂化材料的合成及其圆偏振发光性质开展了系列工作。从合成的角度，手性稀土配合物经过杂化均匀的分布在高分子材料的3D孔道内，打破了配合物的聚集并实现了真实的单分子状态，有效提高了手性稀土配合物的手性光学性质。其次，我们使用价格低廉的手性基团作为手性源获得了发光量子产率高达69%的手性稀土配合物，为制备具有优异发光性能的手性高分子杂化CPL材料有效的降低了成本。从材料的性能方面，通过在手性配体中引入光刺激响应基团或有机荧光小分子使我们获得了具有CPL开/关性能或CPL波长调控的手性高分子CPL材料，为制备多功能手性高分子CPL材料提供了新策略。