氢键参与的超分子镊合识别组装体系

发布时间：2018-03-29 22:20

本文选题：氢键　切入点：主客体识别　出处：《中国科学技术大学》2017年硕士论文

【摘要】：超分子化学是一门研究化学物质通过非共价键相互作用而组装成高度有序的组装体的科学。与传统的共价键化学不同,超分子化学关注的是分子之间的弱相互作用力,主要包括氢键、金属配位、主客体识别、π-π共轭作用和亲疏水作用等。正是由于这些弱的非共价键相互作用具有动态可逆的特点,这些超分子体系通常具有环境响应性。探索新的超分子驱动力以及拓展新型的识别基元,对于超分子化学的发展是非常重要的。在这一方面,铂炔基"镊子型"分子因其具有独特的平面几何结构及迷人的光物理学特性,且能将Pt-Pt金属-金属相互作用与供体-受体作用进行高效加合,做为一种新型的超分子构筑基元而备受关注。本论文在课题组之前关于镊子/芘主客体识别的研究基础上,通过引入分子间O-H---N氢键的作用,以增强镊子主体分子和一系列客体的络合作用,并基于此构筑了含有π-共轭高分子的超分子交联网络,进一步发展了"镊合导向自组装"的策略。主要工作分为以下两个部分:第一部分,我们将氢键作用引入到镊合体系的超分子识别中。我们首先证明了分子间O-H---N的氢键的存在能显著地提高三联吡啶铂炔基镊子主体和一系列萘衍生物的结合强度。并在此基础上,利用"caging"策略将萘衍生物上的氢键供体基团保护起来,成功构筑了多组分的光响应超分子体系。因此,我们实现了通过氢键的参与来远程地调控镊合体系的分子识别,同时这一过程还伴随着有趣的光物理特性的变化,以便发展新型的化学和生物传感器。在第二部分中,我们证明了 "氢键增强镊合体系的主客体识别"可以作为一种很好的策略来构筑新颖的主链型的π-共轭高分子交联网络。聚咔唑高分子能够通过供体-受体和分子间氢键的协同作用部分进入双头镊子的空腔中,形成刺激响应性的三维超分子交联网络,并在高浓度条件下制备了凝胶材料。由于结合了共轭高分子的导电性和凝胶材料的可加工性,有望应用于柔性电子器件等领域。
[Abstract]:Supramolecular chemistry is a science that studies how chemicals are assembled into highly ordered assemblies through noncovalent bond interactions. Unlike traditional covalent bonding chemistry, supramolecular chemistry focuses on the weak interaction between molecules. It mainly includes hydrogen bond, metal coordination, host and guest recognition, 蟺-蟺 conjugation and hydrophilic interaction. These supramolecular systems are generally environmentally responsive. Exploring new supramolecular driving forces and expanding new recognition primitives are important for the development of supramolecular chemistry. Because of its unique planar geometry and attractive photophysical properties, platinylene-based "tweezers" molecules can efficiently adduct Pt-Pt metal-metal interaction with donor-acceptor interaction. As a new type of supramolecular construction unit, this paper has attracted much attention. Based on the previous research on tweezers / pyrene host-guest recognition, we introduce the effect of intermolecular O-H---N hydrogen bond. A supramolecular crosslinking network containing 蟺 -conjugated polymer was constructed based on the enhancement of the complexation between the host molecule of tweezers and a series of guest molecules. The strategy of "tweezers oriented self-assembly" is further developed. The main work is divided into the following two parts: the first part, We introduce hydrogen bonding into supramolecular recognition of tweezers. Firstly, we prove that the existence of hydrogen bonds of intermolecular O-H---N can significantly improve the binding strength of tripyridine platinum alkynyl tweezers and a series of naphthalene derivatives. The hydrogen bond donor group on naphthalene derivatives was protected by "caging" strategy, and a multicomponent photo-responsive supramolecular system was successfully constructed. Therefore, the molecular recognition of tweezers can be remotely regulated by the participation of hydrogen bonds. This process is accompanied by interesting changes in photophysical properties for the development of new chemical and biological sensors. We have proved that "Host-guest recognition of hydrogen Bond Enhancement tweezers" can be used as a good strategy to construct novel host-chain 蟺 -conjugated polymer crosslinked networks. The synergistic effect of the hydrogen bond between molecules enters the cavity of the double-headed tweezers. Three-dimensional supramolecular crosslinking network was formed and gel materials were prepared at high concentration. Due to the combination of the conductivity of conjugated polymers and the processability of gel materials, it is expected to be used in flexible electronic devices and other fields.
【学位授予单位】：中国科学技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3

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