手性烷基链调控下的苝酰亚胺衍生物自组装结构气敏传感性能研究

Chiral amines are very important to life and health of people. Meanwhile, they also bring about some serious environmental pollution due to their excessive using and emission. However, there was not any efficient way to detect chiral amines until now. Our previous studies indicated perylenediimide derivatives (PTCDI) bearing chiral alkyl chain can exhibit better gas sensing properties to amine compounds and are well-suited candidates for the further investigation of high-efficiency devices to detect chiral amines. In this proposal, forty-eight perylene derivatives bearing chiral alkyl chains on the bay- or ortho-regions of perylene core are going to prepare and the responses are going to determine based on their conductometric sensing devices in chiral amine vapour. This study focuses on the effect of length, branched point as well as types of chiral alkyl chain on self-assembled morphologies and sensing properties of assembled nanostructures. On the one hand, it is expected to improve the gas selectivity by strong host (PTCDI)-guest (chiral amines) interaction. On the other hand, it is anticipated to enhance gas response through modulating self-assembled morphologies and aggregated mode. We hope that analysis of the roles of chiral alkyl chains will contribute to a better understanding of the structure-property relationship of organic semiconductor and facilitate the design and improvement of high-performance gas sensing devices.

手性胺类化合物是生命体的物质基础，对人类健康起着至关重要的作用。但近年来手性胺类化合物过度使用和排放，由其引发环境污染问题变得日趋严重，而检测手性胺类化合物手段和方法却十分缺乏。申请人前期研究结果表明，利用苝湾含手性烷基链的苝酰亚胺衍生物（缺电子n型共轭有机分子）传感器电流变化可实现给电子胺类化合物的高效快捷检测。本申请拟制备两类共四十八种苝湾和邻位碳原子含手性烷基的链苝酰亚胺衍生物，研究其组装体在手性胺类化合物气氛下气敏传感性能。一方面利用苝酰亚胺衍生物与手性胺类化合物主客体识别作用提高其气敏选择性，另一方面借助烷基链下影响下的分子间手性诱导、亲疏水、范德华力和π-π相互作用调控苝酰亚胺衍生物宏观组装形态和微观堆积方式，改善其气敏响应性，研究并揭示手性烷基链位置、构型、长度、支链点等对苝酰亚胺衍生物组装体气敏传感性能的影响规律，为制备高性能苝酰亚胺衍生物气敏传感器提供理论依据和物质基础。

近年来，由胺类化合物过度使用和排放引发地环境污染问题变得日趋严重，而检测胺类化合物手段和方法却十分缺乏。苝酰亚胺衍生物作为一类缺电子n型共轭有机分子，可与富电子胺类气体发生电子传递引起其电流变化，从而实现胺类化合物高效快捷检测。本课题通过共价键和离子键作用在苝酰亚胺衍生物苝湾位置和酰胺氮原子位置引入手性烷基链，给电子脂肪烃和芳香烃，吸电子硝基和硫族原子制备了两类共20种苝酰亚胺衍生物，构筑其电阻式气敏传感器，通过电流变化，评价其在氨气、乙二胺和水合肼气体中的气敏传感性能研究。研究结果揭示：（1）手性苝酰亚胺衍生物因组装体具有规则连续微观聚集结构，呈现较优异气敏传感性能；（2）苝酰亚胺衍生物通过能级结构影响其气敏稳定性，通过能级结构和立体异构变化，调控其气敏选择性；（3）苝酰亚胺衍生物通过分子间重叠面积和分子间距影响气敏灵敏度。该课题系统研究并揭示取代基类型和位置对苝酰亚胺衍生物气敏传感性能的影响规律，建立了分子结构调控苝酰亚胺衍生物气敏传感性能的方法和理论，为制备高性能有机半导体气敏传感器提供了理论依据和物质基础。