基于供受体驱动力的新型超分子聚合体系研究

Supramolecular polymers represent a novel class of macromolecules, in which the monomeric units are held together by noncovalent interactions. Currently, hydrogen bonding, metal-ligand coordination and macrocyclic host-guest interactions have been widely utilized to drive the supramolecular polymerization process, due to their high complexation directionality, strong binding affinity and stimuli-sensitive responsiveness. The expansion of new driving forces for fabricating novel supramolecular polymer materials is one of the hot research topics in supramolecular chemistry. Comparing with the traditional non-covalent driving forces mentioned above, donor-acceptor charge-transfer interactions have some unique advantages, such as wider solvent tolerance, versatile building blocks, easy spectroscopic probing and so on. However, low association constant, poor complexation directionality and deficient stimuli-responsiveness limited their applications as the main driving force for the fabrication of supramolecular polymer materials. In order to overcome the shortages as mentioned above, herein the novel macrocyclic host are designed and constructed, in which two pieces of alkynylplatinum(II) terpyridine complex were employed as the electron-deficient pincers, and that could complex the electron-rich guest with enhanced association constant and high complexation directionality. Such a protocol ensures the positioning of various π-aromatic moieties with molecular-level precision and results in well-defined and unique photo response supramolecular polymer gels, which are promising for optoelectronic applications. The results and strategy of the current project will provide novel methodology for developing supramolecular materials.

探索新型的非共价键驱动力，并用于构筑超分子聚合物材料是目前超分子科学领域研究的热点之一。目前用于构筑超分子聚合物的非共价键驱动力主要有三类：多重氢键作用力，金属配位作用力以及主客体络合作用力。相比于上述传统的非共价键驱动力，电子供受体相互作用力具有良好的溶剂耐受性、构筑基元来源广泛性以及结合过程可以通过光谱学信号来进行有效地跟踪与检测等优点。然而，供受体作用力结合方向性差、结合强度低以及刺激响应性相对缺乏等缺陷，限制了其作为主要的非共价键驱动力用于超分子聚合物材料的构筑。为了克服上述缺陷，本项目拟将供受体相互作用与主客体相互作用高效复合，构建新型基于三联吡啶铂（II）炔基元的大环主体结构，并用于结构规整且具有独特光响应特性的超分子聚合物凝胶材料的构筑，为其在光电功能材料领域提供潜在的应用价值。本项目的研究为发展新型的基于电子供受体相互作用驱动的超分子聚合物材料提供新的思路。

发展新型的共价键作用力构筑超分子聚合物材料是超分子化学领域中重要的研究方向。本项目中，申请人利用金属与联吡啶配体为基本构筑基元，构筑具有刺激响应性的超分子聚合物材料，并探索其潜在的应用价值。本项目分为两个研究部分：.在第一部分的研究中，申请人将联吡啶铂炔配合物作为基本的功能基元，链接在二苯基吡啶分子骨架上形成分子镊子结构。通过一价铜离子的桥联以及π-π、Pt(II)-Pt(II)相互作用构筑超分子组装体。同时，所构筑的超分子组装体结构具有良好的光热转换特性。.在第二部分的研究中，申请人将三联吡啶与金属之间的配位作用作为基本的非共价键驱动力，通过功能基元的引入构筑具有刺激响应性的超分子聚合物材料，并展示出良好粉发光特性。本项目的实施，是发展非共价键驱动力构筑超分子聚合物新的尝试，为超分子功能材料提供新的参考。

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