近红外光响应的类酶镧系金属-有机超分子光催化剂的开发及性能研究

As a clean, efficient and economical route for the production of organics, photocatalysis has drawn extensive attention due to its potential application in tackling energy and environmental problems. Metal-organic supramolecular assemblies display high catalytic selectivity in photoredox catalysis. But still, their wide application is largely limited by the low turnover, and ultraviolet-/visible-light stimuli. So it is important to develop supramolecular photocatalysts with high catalytic activity, selectivity and near-infrared light (NIR) stimuli ability. Based on the previous study and experimental results, we found that the cooperative action of supramolecular microenvironment and catalyst results in efficient turnover elevation. Moreover, supramolecular host-guest complexation is conductive to efficient triplet-triplet annihilation upconversion (TTA-UC), which converts low-energy photons into high-energy excited states and further enabled the direct activation of substrates by NIR light. Based on the above ideas, we focus on the design and synthesis of porphyrin functionalized lanthanide-organic supramolecular assemblies with high triplet fusion upconversion efficiency and photocatalysis activity, and study the specific recognition of guests and pairwise encapsulation of photoredox annihilator and substrates by the cationic supramolecular cages. We intend to reveal the key influencers that affect the photoredox activity through theoretical simulations and quantum chemical calculations.

光催化转化是一种清洁、高效、经济的有机合成手段，在解决能源短缺和环境污染等方面展现出巨大的应用前景。金属有机超分子纳米容器能够实现较高的光催化反应选择性，但反应转化率低、需要用紫外光或可见光激发，大大限制了其适用范围和光能利用率。调研发现，超分子特性和催化剂的协同催化效应能够大大提高催化反应转化率，且超分子主客体相互作用有利于实现高效的三重态-三重态湮灭上转换，将能量较低的长波长光转换为能量较高的短波长光，实现近红外光催化转化。基于以上研究思路，本项目设计合成卟啉基镧系金属-有机超分子组装体，探究此类阳离子型纳米容器对特定底物分子特异性识别以及对具有激发单重态氧化还原活性的受体分子和底物分子的选择性成对封装规律，基于三重态-三重态湮灭上转换发展具有较高反应转化率和近红外光催化活性的超分子光催化剂，并结合理论模拟和量化计算揭示影响光催化性能的因素。

配位导向自组装能够以简单结构基元为基础构筑结构复杂、功能多样的组装体，实现了对自然有机功能体的高度模拟。镧系金属-有机超分子组装体具有较好的光学活性和纳米尺寸的疏水性空腔，在光响应材料和类酶催化材料方面具有潜在的应用价值。本项目采用配位导向自组装的方法，在配体中引入卟啉或炔基铂等具有光功能活性的官能团，与镧系金属离子通过配位自组装制备得到一系列具有较好光学活性的镧系金属-有机超分子笼。利用分子笼较大的疏水性空腔，实现了对不同种类底物分子的识别和封装。利用底物分子和分子笼之间的相互作用以及分子笼自身的催化性能实现了特定底物分子高效高选择性的催化转化。项目执行三年来，对设计合成具有优异光学传感特性和类酶催化性能的新型镧系金属-有机超分子材料做了有益的探索，并取得了一些有价值的研究成果。项目部分成果共发表SCI收录的论文9篇，申请国内发明专利1项。

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