新型双活性位点手性可见光催化剂的设计合成和结构调控

Asymmetric photocatalysis is a very attractive and challenging research topic and the development of chiral photocatalysts is the heart. So far, only a few chiral photocatalysts with low quantum yields of photoinduced electron transfers and limited light utilization efficiencies are available. To promote the development of asymmetric photocatalysis, a series of BINOL/naphthaleneimide based chiral metal complexes containing two active sites of Lewis acid and π acid will be designed and synthesized in this project. Such unique complexes are anticipated to be a class of interesting visible-light driven chiral photocatalysts for the asymmetric photocatalysis since they combine the asymmetric catalytic function of BINOL-based complexes with the visible-light photocatalysis of rylene imides. Then, their synthetic methods, physical-chemical properties (optical, electrochemical and photoinduced electron transfers, etc.), supramolecular behaviors (molecular recognitions, supramolecular structures and properties, etc.) as well as photocatalytic activities will be carefully studied. The effects of their structures (e.g. peripheral substituents and metal ions) on their selective recognitions, photoinduced electron transfers and photocatalytic activities will be focused, and thus the structure-activity relationship will be demonstrated. In addition, their structure-tuning laws are anticipated to be sorted out and photocatalytic mechanisms will be finally disclosed. This research is anticipated to provide a theoretical and experimental basis for the highly effective and selective chiral visible-light photocatalysts using in asymmetric photocatalysis.

不对称光催化合成是极具诱惑力和挑战性的研究课题，其核心是手性光催化剂。针对现有可用手性光催化剂存在的电子转移效率低和太阳能利用率不高等问题，本项目拟设计合成系列兼具联萘酚金属配合物的手性催化与稠环芳酰亚胺衍生物的可见光催化两种功能的，含有金属离子Lewis酸与萘酰亚胺π-酸两种活性位点的联萘酚/萘酰亚胺基手性金属配合物，作为不对称光催化合成的新型手性可见光催化剂；研究其合成方法、理化性质（光谱、电化学和光诱导电子转移等）、超分子化学行为（分子识别、超分子复合物结构与性质等）以及不对称光催化有机合成性能；重点考察其结构（周环取代基与金属离子等）对分子识别能力、光诱导电子转移性质和光催化性能等的影响，阐明它们之间内在联系，总结其结构调控规律，并揭示其作用机理。本项目研究结果将为设计合成新型的高效和高选择性不对称光催化合成用手性可见光催化剂提供理论和实验依据。

不对称光催化合成是极具诱惑力和挑战性的研究课题，其核心是手性光催化剂。针对现有可用手性光催化剂存在的电子转移效率低和太阳能利用率不高等问题，本项目成功合成了一系列含有联萘酚和稠环酰亚胺两种官能团的手性配体，与金属离子（含过渡金属和稀土金属离子）的配位组装，得到一类含有金属离子Lewis酸与稠环酰亚胺π-酸两种活性位点的新型手性金属配合物，详细表征了中间体及目标产物的化学结构，计算了其电子结构，研究了它们的理化性质（吸收和荧光光谱以及电化学等）、超分子化学行为（分子识别、超分子复合物结构与性质等），探讨了其结构与性质之间内在联系。与此同时，对所得中间体以及配合物的光诱导电子转移性能进行重点研究，考察了其结构对光诱导电子转移性能的影响，阐明它们之间内在关系，总结其结构调控规律。在此基础上，对所得配合物在光催化不对称合成领域应用进行探索，初步揭示了催化作用机制，为设计高效和高选择性的手性光催化剂提供理论和实验依据。在项目执行期间本学科相关国际期刊上发表文章27篇，授权国家发明专利1件，培养7名研究生，达到了研究的预期目标。