Iminoboronate Polymers as Dynamically Adaptable, Photoactive Materials

含有动态共价键的聚合物形成了一类“智能”材料，能够适应或能够响应应用的化学或环境刺激而改变。我们提出了一类基于可逆亚硼酸酯键基序的动态共轭聚合物。含有醛，胺和硼酸功能的简单ab型单体将与二醇一起聚合产生亚氨基硼酸酯聚合物。正交动态亚胺和硼酸酯键的存在将使我们能够开发易于功能化，因此可调的多组分聚合物材料，这些材料具有重组或适应各种外部刺激的能力。通过加入电子上不同的二醇，共轭聚酰亚胺聚合物主链的光物理性质可以调整，为获得所需的材料性质提供了可预测的途径。该材料系统的独特特性-高度可调谐的电子性能，通过与偶联N-B稳定的结构刚性和由于非共轭硼功能化的电化学稳定性-有望使这些聚合物成为发光器件的有力候选者。（此外，获得亚氨基硼酸盐对电子上不同的二醇的亲和力的基本理解将使我们能够通过连续的二醇交换来促进聚合物性质的连续变化。）这些材料将被研究作为特定二醇的荧光多受体，以及作为可控制的交联或去交联材料，添加或置换紫杉醇。这些高价值智能材料的开发将为下一代多功能设备奠定基础，例如具有卓越效率和电化学稳定性的蓝光发光聚合物，而不是最先进的聚芴oled。

Polymers incorporating dynamic covalent bonds form a class of "smart" materials that are able to adapt to-or can be altered in response to-applied chemical or environmental stimuli. We propose a new class of dynamic, conjugated polymers based on the reversible iminoboronate ester bonding motif. Simple AB-type monomers incorporating aldehyde, amine, and boronic acid functionalities will polymerize together with diols to produce iminoboronate ester polymers. The presence of orthogonal dynamic imine and boronate ester bonds will allow us to develop easily functionalizable, and thus tuneable, multicomponent polymer materials that possess the ability to reorganise or adapt in response to various external stimuli. By incorporating electronically distinct diols, the photophysical properties of the conjugated polyimine polymer backbone may be tuned, providing a predictable pathway for attaining desired material properties. The unique set of characteristics of this materials system - highly tuneable electronic properties, structural rigidity through dative N-B stabilisation and electrochemical stability due to non-conjugated boron functionalization - promise to make these polymers strong candidates for light-emitting devices. (Additionally, obtaining a fundamental understanding of the affinity of the iminoboronate for electronically different diols will allow us to promote consecutive changes in polymer properties through successive diol exchanges.) These materials will be investigated as fluorescent polyreceptors for specific diols and as controllably crosslinkable or decrosslinkable materials with the addition or displacement of tetrols. Development of these high-value smart materials will lay the groundwork for the next generation of multifunctional devices, such as blue-light-emitting polymers with superior efficiency and electrochemical stability to the state-of-the-art poly(fluorene) OLEDs.