新型远程调控光电活性受体的超分子识别与组装研究

In this project, novel ferrocene- and anthraquinone-bridged thiacalix[4]crown receptors incorporating diverse remotely-tunable functional groups will be designed, based on the principles of molecular recognition, synthesized using click reaction as the key step, and fully characterized by 1H NMR, 13C NMR, IR, MS and elemental analyses, as well as X-ray diffraction techniques. The supramolecular recognition properties of such receptors will be systemically investigated via optical and electrochemical approaches so as to establish the experimental methods and theory to further design new optical- and redox-active receptors with higher selectivity for sensing some environmentally and biologically relevant ionic species and to assemble nanosupramolecular devices with specific functions. In addition, the new remotely-tunable effect of these receptors will be explored. The remotely-tunable thiacalix[4]crown receptors with unique structures designed in this project, are the vital candidates for electrochemical and optical recognition receptors. They are expected to exhibit very excellent electrochemical recognition and fluorescent responsive properties, and to display potential applications for developing the new supramolecular devices that possess specific functions because the ferrocene and anthraquinone probes have good electrochemical and optical behavior, while thiacalix[4]crowns are unique and tunable organic supramolecules with three-dimensional structures. Our work is greatly significant for designing and making new materials, including nanomaterials, and for developing supramolecular chemistry.

本项目基于分子识别原理，以硫杂杯[4]芳烃为构建平台、二茂铁和蒽醌等为信息转换中心，利用新兴的click技术，设计合成具有不同远程调控基团的新型光电活性硫杂杯[4]芳烃冠醚受体；以在生命、环境和光电材料中具有重要意义的离子作为目标底物，系统研究这些受体的超分子识别功能、组装纳米尺寸的超分子器件、探索远程调控效应、总结适配规律、阐明作用本质，为研制具有光、电双通道检测功能的高选择性超分子受体和组装具有特定调控功能的超分子器件提供理论依据和实验方法。本项目的特色是超分子受体的结构设计新颖独特，通过click技术引入性能优异的荧光和电化学活性功能基，组装具有开放三维结构与调控功能的光、电活性纳米级超分子体系，可望有效提升对某些目标底物的选择性电化学识别和荧光传感水平，发现具有新功能的超分子器件，对新材料的开发和超分子化学的发展具有重要理论和实际意义。

本项目基于分子识别原理研究了新型远程调控光电活性识别受体的构建方法。以click反应为关键技术，以硫杂杯[4]芳烃为构建平台，二茂铁、罗丹明和蒽醌等为信息响应中心，设计、合成了一系列具有远程调控功能的光电活性硫杂杯[4]芳烃冠醚和开链多醚受体；分别采用单、双Ugi四组分反应设计、合成了一系列光电活性二茂铁双酰胺类受体；基于不同桥联基团设计、合成了一系列光电活性二茂铁-罗丹明受体；研究了光电响应中心一体化的构建方法。受体的化学结构均经IR, 1H NMR, 13C NMR、MS和元素分析所表征，并利用X-射线衍射分析和Hirshfeld表面分析技术研究了代表性受体和关键中间体的晶体结构及其超分子组装。经紫外可见光谱、荧光光谱和电化学研究，发现这些受体具有新奇的光电性质，对Pd2+、Zn2+、Pb2+、Hg2+、Cu2+、Fe3+等离子具有优异的光电识别功能，部分受体可作为优良的荧光探针应用于高效细胞成像检测。分析总结了远程调控效应，通过理论计算初步阐明了其作用本质，为设计、合成具有远程调控功能的光电双通道检测超分子受体提供了理论依据和实验方法。本项目所设计合成的超分子受体结构新颖独特，对特定底物具有优异的光、电响应与多通道识别功能，具有丰富的超分子组装模式，通过远程调空可有效提升对特定底物的识别选择性，对新材料的开发和超分子化学的发展具有重要理论意义和应用前景。