光可控的多吡啶铂(II)配合物超分子组装体的设计合成及应用研究

Self-assembly refers to the construction of stable and orderly structures through intermolecular interactions of the building blocks, which is an important way of creating new materials and functions. The control of self-assembly process is the key to construct intelligently and responsively supramolecular self-assembly systems. In this proposal, a series of amphiphilic binuclear platinum(II) polypyridyl complexs beared light-responsive stiff stilbene will be rationally desgined and synthesized as building blocks to construct light-responsive supramolecular assemblies, together with the control of structures and functions of the assemblies by different light wavelengths. The substitution of stiff stilbene and hydrophilic chains on the platinum(II) complexes will be investigated to reveal the influence on the morphologies and photophysical properties of the assemblies with different structures. By changing different light wavelengths, the relationship between the mophologies and photophysical properties of the assemblies and the structures of the building blocks would be investigated in order to control the structures and functions of the supramolecular assemblies. On this basis, the supramolecular assemblies would be further explored as the potential application in drug delivery. It is envisaged that these results will provide beneficial understanding for the self-assembly process and preparing functional supramolecular systems based on platinum(II) polypyridyl complexes.

自组装是指构筑基元通过分子间相互作用而形成的稳定有序结构，是创造新物质和产生新功能的重要手段；如何通过某种手段对自组装过程进行调控，是构筑智能响应性超分子自组装体系的关键。本项目拟设计合成含有光响应的刚性二苯乙烯基团连接的两亲性双核多吡啶铂(II)配合物作为组装基元，构筑具有光响应性的超分子组装体，通过控制光照的波长而实现对组装体结构和功能的调控。通过变换组装基元多吡啶铂(II)配合物中刚性二苯乙烯和亲水性侧链的位置，研究不同结构的组装基元对所形成组装体的形貌结构以及光物理性质等的影响。通过变化不同的光照波长，研究所得组装体由于构筑基元分子构型的改变而导致其形貌结构和光物理性质等的变化规律，实现对超分子组装体结构及功能的调控。在此基础上，初步探索该类超分子组装体在药物传递等方面潜在的应用。研究结果将为实现自组装过程的调控及制备功能导向的多吡啶铂(II)配合物超分子体系提供有益的探索。

本项目以设计合成具有特定功能的组装基元为主线，开展工作如下：（1）将亲脂性侧链引入到多吡啶铂(II)配合物构筑基元中，其在有机溶剂中组装形成小分子凝胶，该类凝胶可以实现对外界刺激如温度、超声、离子等的可逆响应；（2）将亲水性侧链引入到多吡啶铂(II)配合物构筑基元中，实现其在水溶中组装形成胶束、囊泡的结构，该类组装体可以在外界刺激的响应下实现组装结构和激发态的有效调控；（3）以具有聚集诱导发光效应的基团（如四苯乙烯等）为分子骨架，利用主体包裹增强的π-π堆积相互作用构筑超分子聚合物，其可以在水溶液中自组装形成球形聚集体、纳米棒等结构，利用该类超分子聚合物可以实现水溶液中高效光捕获体系的构筑；（4）利用超分子自组装的思路，采用化学还原法，诱导石墨烯通过片层结构之间的π-π堆积和范德华力相互作用，形成具有三维多孔结构的新型三维石墨烯，在能源存储等方面体现出优良的性能。总之，我们不仅构筑了以多吡啶铂(II)配合物为功能核心单元的超分子组装体系和具有聚集诱导发光效应的超分子聚合物，并拓展了其他功能超分子体系和材料以及它们的应用；这些研究结果为设计合成新型功能性超分子体系和材料奠定了一定的基础，共发表SCI论文17篇。