稀土多核配合物的识别功能及其应用研究

The research on the functionalization of rare-earth complexes has attracted more and more attentions in chemistry, biomedicine, materials science, and environmental science. On the basis of our previous researches, several series of novel organic bridging ligands and polynuclear rare-earth complex recognition systems will be designed and synthesized based on the combining with superior performance of polynuclear rare-earth complexes and recognition function of supramolecular systems. Single or multiple identification signals will be modulated by changing the structures of polynuclear complexes and external conditions, and the detection selectivity for metal ions, anions, small molecules and biological macromolecules will be investigated. Furthermore, the multifunctional nano-composite materials of polynuclear rare-earth complexes will be fabricated and researched for multimodal imaging, detecting of cancer markers and controlling drug release. A series of polynuclear rare-earth complexes molecular devices with excellent performance of novel sensing and switches will be screened out, and the applications in environmental monitoring and biological systems will be explored in detail. Through the studies, we will establish the method to design and fabricate the recognition systems of rare-earth complexes, explore the collaborative recognition effects and mechanisms, and summarize the relationships between structures and properties. The research achievements will provide the important theoretical basis for the design and application of functional materials. We expect that fifth to eighty top-quality papers could be published in famous journals including J. Am. Soc. Chem., Angew. Chem. Int. Ed. and Adv. Mater., some patents could be applied by the relative researches, and twenty to thirty graduate students will be brought up by the project implement.

稀土配合物功能化研究是化学、生物、材料及环境等学科的热点前沿。本项目在已有工作基础上，结合稀土多核配合物的优良性能和超分子体系的识别功能，设计合成桥联配体，组装稀土多核配合物识别体系；通过改变配合物结构及外部条件调制配合物的单重或多重识别信号，测试其对离子、小分子和生物大分子的识别性能；研究稀土多核配合物多功能纳米复合物对癌症标志物的多模式成像和检测效果及药物控释；筛选出具有优良识别性能的稀土多核配合物分子器件，探索其在环境监测和生物医学中的应用。建立稀土多核配合物识别体系的设计和构筑方法，探讨协同识别效应和识别机理，总结构效关系，为新型稀土多核配合物功能材料的设计应用提供理论参考。预期可在J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater.等刊物上发表高质量学术论文50-80篇，有关成果申请专利。培养博士、硕士研究生20-30名。

本项目立足于稀土配合物的结构和功能研究，利用稀土离子特殊的配位方式和优良的性能，设计合成了多种类型的有机配体、一系列不同核数和不同结构的稀土多核、杂多核配合物、稀土有机框架配位聚合物；研究了多稀土中心配合物体系的构筑方式、自组装条件和特点、复杂配合物体系识别机理、功能稀土配合物传感响应和稀土多金属位点催化作用；考察了基于稀土配合物与各种材料的主-客体相互作用，筛选和优化了各种识别基团及识别机理，提升了稀土配合物识别功能的响应效率；构建了不同功能的稀土配合物复合材料，实现了稀土配合物从简单分子向复杂材料拓展，从单一功能分子向多功能纳米尺度荧光探针拓展，从分子层次向多层次、多维度信息存储和防伪功能智能光学信息存储材料拓展，从单一响应向多刺激响应（包括光、热和酸碱性气氛等）拓展，从可见发光向近红外光驱动的双光子智能诊疗探针拓展，最终实现了稀土配合物在功能材料、生物医学、防伪成像、分子催化等领域中的应用，这对稀土配合物分子结构的认识和稀土资源的高值化应用具有重要的科学意义，为丰富配位化学研究内容提供支撑。本项目已实现申请时的目标，项目组已在J. Am. Soc. Chem., Angew. Chem. Int. Ed., Adv. Mater., Nat. Commun., Chem. Commun., Chem. Eur. J., Inorg. Chem., Dalton Trans., Anal. Chem., Green Chem., Sci. China: Chem., J. Mater. Chem. A/B/C, ACS Appl. Mater. Interfaces等刊物上已发表SCI收录论文共162篇，其中21篇论文期刊影响因子>9.0，66篇论文在JCR一区刊物；10篇有关稀土多核结构构筑及性能研究论文被编辑部遴选为内封面或封底文章重点介绍，4篇有关稀土复合材料及其药物控释研究论文被编辑部遴选为封面文章；受邀撰写综述文章4篇，系统总结课题组工作及近年来在稀土发光配合物以及稀土功能材料研究进展；授权国家发明专利8项；项目组成员受邀参加会议并作主题报告和邀请报告共计56人次，并主办6次学术会议进行学术交流；项目组1名成员入选教育部“长江学者”奖励计划特聘教授；项目组负责人获宝钢优秀教师奖和卢嘉锡优秀导师奖。