基于酰肼的自组装环形六聚体的功能化

The current proposal is based on the self-assembled cyclic hexamer from hydrazide hydrogen bonding units that we previously reported. (1) In addition to intramolecular hydrogen bonding strategy for precise control, we want to develop new strategies of fabrication of hydrophobic/hydrophilic property of the side chains and guest recognition to achieve dynamic, reversible and stimuli-responsive regulation. (2) Functionalization of the self-assembly entity will be achieved by attaching electroactive ferrocene unit and fluorescent pyrene and perylene units to the vertex of the monomers. Investigation of the electron communication among metal centers and fluorescence resonance energy transfer among fluorescent groups will lay solid base for the construction of functional materials. (3) Nanotube structure will be constructed by attaching bifurcated hydrogen bonding unit and large planar conjugated motifs to the vertex of the monomers driven by hydrogen bonding and π-π interaction respectively. Their potential applications in photoelectric material, liquid crystal, material transportation etc. will be explored. Dynamic and stimuli-responsive control of the self-assembly process can be achieved by successful implementation of the proposal. Based on the investigation of structures, we will provide new ideas and platforms for the construction of new materials.

本申请课题以我们前期构筑的基于酰肼氢键键合单元的自组装环形六聚体为研究对象。（1）在分子内氢键策略精确调控自组装过程的基础上，我们拟通过改变侧链亲疏水性和客体识别两种策略实现对自组装过程动态可逆和外界刺激响应性调控。（2）在单体结构中引入电活性的二茂铁单元以及苝和芘荧光单元，实现组装体的功能化，研究组装体金属中心之间的电子传输和荧光基团之间的荧光共振能量转移，为新型材料的构筑打下基础。（3）在单体顶点位置引入三中心氢键键合单元和大的平面共轭体系，通过氢键和π-π堆积作用驱动构筑纳米管道，并研究管道在光电材料、液晶、物质传输等领域的实际应用。本申请课题的成功实施，将实现对自组装过程的动态调控，并在结构研究的基础上，为新材料的研发提供新的思路和平台。

本课题系统的发展了功能化多氢键环形六聚体的方法。（1）在组装单体的顶点位置，通过炔键、Pt-N配位和酰胺键将芘和苝荧光基团引入，使得组装体具有荧光特性，并且通过基激缔合物-单体荧光信号转换和荧光共振能量转移（FRET），系统研究了组装过程的动力学。（2）将电活性单元——二茂铁，通过三种键连方式：炔键，N-Pt配位键和炔键-Pt-炔键引入到环形顶点位置，构筑具有多金属中心的组装体。（3）分别在端基和顶点位置引入手性辅助因素，诱导组装过程新的超分子手性的形成。这些研究有助于加深对多氢键自组装过程的深刻理解，并为其进一步应用打下良好的基础。